Cosmetic process for making-up and/or caring for the skin and/or the lips

ABSTRACT

A cosmetic process for making-up and/or caring for skin and/or lips, includes the application to skin and/or lips of a cosmetic composition including, in a physiologically acceptable medium, at least one supramolecular polymer and at least one hydrophobic film-forming polymer. Particular compositions may be used in the process.

This is a Division of application Ser. No. 13/700,029 filed Jan. 20,2013, which in turn is a National Phase Application ofPCT/IB2011/052281, filed May 25, 2011, which claims the benefit of U.S.Provisional Application No. 61/344,148, filed Jun. 1, 2010 and FR1002234, filed May 26, 2010. The disclosure of the prior applications ishereby incorporated by reference herein in its entirety.

The present invention relates to a cosmetic process for making up and/orcaring for the skin and/or the lips, comprising at least the applicationto the said skin and/or the said lips of a cosmetic compositioncomprising, in a physiologically acceptable medium, at least onesupramolecular polymer and at least one hydrophobic film-formingpolymer. The invention also relates to particular compositions that maybe used in the process of the invention.

In general, when women use a makeup product, especially of foundationtype, they wish this product to have, after application, good remanenceon the skin, and in particular for it not to transfer onto clothing.

With regard to this expectation, one or more polymers that arespecifically dedicated towards affording these improved remanenceproperties over time are commonly introduced into compositions of thistype. Illustrations of these polymers that may particularly be mentionedinclude polyacrylates and latices.

However, the abovementioned polymers that are advantageous in terms ofremanence properties, and in particular of transfer resistanceproperties, are unfortunately liable to give rise to a sensation ofdiscomfort during application (difficult, tacky spreading) and/or afterapplication (tautness, mask effect) of the cosmetic product containingthem.

On the other hand, supramolecular polymers such as those described inpatent applications EP 2 189 151 and FR 2 938 758 are known for allowingthe production on the skin of a deposit that is both comfortable andendowed with good remanence properties. However, deposits formed from agalenical formulation incorporating such a supramolecular polymer mayhave insufficient mechanical strength (which may be reflected bystaining of clothing). Moreover, their contact with fatty substances,for example a food oil in the case of a lipstick applied to the lips,may affect their integrity.

Consequently, there is still a need to overcome these drawbacks asregards galenical formulations based on supramolecular polymer.

The aim of the present invention is to overcome these drawbacks and topropose a cosmetic composition that is capable, on the one hand, ofaffording good cosmetic properties such as good adhesion to the support(skin) and thus good remanence of the composition, where appropriategood sheen, and, on the other hand, of forming a non-tacky or sparinglytacky deposit that is particularly resistant to external attack by fattysubstances (oil, meals or sebum) and also to friction, resulting in lesswear of the deposit.

The inventors have found, unexpectedly, that it turns out to be possibleto satisfy this aim provided that such supramolecular polymers are usedin combination with a hydrophobic film-forming polymer.

Thus, according to one of its aspects, the invention relates to acosmetic process for making up and/or caring for the skin and/or thelips, comprising at least the application to the said skin and/or thesaid lips of a composition comprising, in a physiologically acceptablemedium, at least one supramolecular polymer based on a functionalizedpolyalkene of formula HO—P—OH in which P represents a homopolymer or acopolymer that may be obtained by polymerization of one or more linear,cyclic and/or branched or polyunsaturated C₂-C₁₀ and preferably C₂-C₄alkenes, which may be derived from the reaction, especially thecondensation, of the said functionalized polyalkene polymer with atleast one junction group functionalized with at least one reactive groupcapable of reacting with the reactive group(s) of the functionalizedpolyalkene polymer, the said junction group being capable of forming atleast 3H (hydrogen) bonds, preferably at least 4H bonds, preferentially4H bonds, and at least one hydrophobic film-forming polymer.

For the purposes of the present invention, the term “physiologicallyacceptable medium” is intended to denote a medium that is suitable forthe application of a composition to the skin or the lips, in particularthe skin and especially of the face.

For the purposes of the present invention, the term “hydrophobicfilm-forming polymer” is intended to denote a film-forming polymer thathas no affinity for water and, in this respect, does not lend itself toformulation in the form of a solute in an aqueous medium.

As emerges from the foregoing text, the hydrophobic film-formingpolymers that are suitable for use in the invention may be chosenadvantageously from polyamide silicone block polymers, block ethylenicpolymers, vinyl polymers comprising at least one carbosiloxane dendrimerderivative, copolymers comprising carboxylate groups andpolydimethylsiloxane groups, silicone resins and lipodispersiblepolymers in the form of a non-aqueous dispersion of polymer particles,and mixtures thereof.

Advantageously, the compositions under consideration according to theinvention are anhydrous or contain less than 3% by weight of water andpreferably less than 1% by weight of water relative to the total weightof the composition.

The term “anhydrous” especially means that water is preferably notdeliberately added to the composition, but may be present in traceamount in the various compounds used in the composition.

As emerges from the examples hereinbelow, the combination underconsideration according to the invention proves to be most particularlyeffective for increasing the resistance of the deposit formed onapplication to the skin or the lips from the corresponding cosmeticcomposition. The deposit thus obtained has improved remanence andsignificantly reduced affinity for the fatty substances with which it isliable to come into contact. Its transfer-resistance properties aremoreover significantly improved. In addition, such a depositadvantageously proves to be sparingly tacky or even non-tacky.

This particular embodiment may thus especially allow the production ofcompositions, especially makeup compositions, whose deposition onkeratin materials, and in particular the lips and/or the skin, isuniform and/or sparingly tacky or non-tacky. Such a deposit mayespecially afford a sensation of comfort to the wearer (softness,glidance of the deposit formed).

In addition, such a composition may have improved properties in terms oftransfer resistance, remanence of the deposit, especially in terms ofcolour (no embrittlement or fragmentation of the deposit, which remainsuniform and/or resistant to friction), and of resistance to fats.

Thus, according to another of its aspects, the present invention relatesto a composition for making up and/or caring for the skin and/or thelips, comprising, in a physiologically acceptable medium, at least onesupramolecular polymer as defined above, at least one hydrophobicfilm-forming polymer and at least one pigment different from a nacre andfrom black iron oxide.

According to another of its aspects, the present invention relates to acomposition for making up and/or caring for the skin and/or the lips,comprising, in a physiologically acceptable medium, at least onesupramolecular polymer as defined above, and at least one copolymercomprising carboxylate groups and polydimethylsiloxane groups.

According to another of its aspects, the present invention relates to acomposition for making up and/or caring for the skin and/or the lips,comprising, in a physiologically acceptable medium, at least onesupramolecular polymer as defined above, at least one hydrophobicfilm-forming polymer and at least 1% by weight relative to the totalweight of the said composition of at least one organic or inorganicfiller.

According to another of its aspects, the present invention relates to acomposition for making up and/or caring for the skin and/or the lips,comprising, in a physiologically acceptable medium, at least onesupramolecular polymer as defined above, at least one hydrophobicfilm-forming polymer and at least one oil other than isododecane andcyclopentadimethylsiloxane, in particular a non-volatile oil andpreferably at least one silicone oil.

According to another of its aspects, the present invention relates to acomposition for making up and/or caring for the skin and/or the lips,comprising, in a physiologically acceptable medium, at least onesupramolecular polymer as defined above, at least one hydrophobicfilm-forming polymer and at least 4.5% by weight of ethanol relative tothe total weight of the said composition.

According to another of its aspects, the present invention relates to acomposition for making up and/or caring for the skin and/or the lips,comprising, in a physiologically acceptable medium, at least onesupramolecular polymer as defined above and at least one polyimidesilicone block polymer.

According to another of its aspects, the present invention relates to acomposition for making up and/or caring for the skin and/or the lips,comprising, in a physiologically acceptable medium, at least onesupramolecular polymer as defined above and at least one vinyl polymercomprising at least one carbosiloxane dendrimer derivative.

According to another of its aspects, the present invention relates to acomposition for making up and/or caring for the skin and/or the lips,comprising, in a physiologically acceptable medium, at least onesupramolecular polymer as defined above and at least one lipodispersiblepolymer in the form of a non-aqueous dispersion of polymer particles.

According to another of its aspects, the present invention relates to acomposition for making up and/or caring for the skin and/or the lips,comprising, in a physiologically acceptable medium, at least onesupramolecular polymer as defined above and at least 5% by weight of oneor more block ethylenic polymers relative to its total weight.

In particular, the present invention relates to a composition for makingup and/or caring for the skin and/or the lips, comprising, in aphysiologically acceptable medium, at least one supramolecular polymeras defined above, at least one block ethylenic polymer and at least oneorganic or inorganic filler.

According to another embodiment, the present invention relates to acomposition for making up and/or caring for the skin and/or the lips,comprising, in a physiologically acceptable medium, at least onesupramolecular polymer as defined above, at least one block ethylenicpolymer and at least one pigment other than a nacre.

The present invention relates to a composition for making up and/orcaring for the skin and/or the lips, comprising, in a physiologicallyacceptable medium, less than 4.5% by weight of ethanol, in particularless than 2% by weight of ethanol or even less than 1% by weight ofethanol, at least one supramolecular polymer as defined above and atleast one block ethylenic polymer.

The present invention also relates to a composition for making up and/orcaring for the skin and/or the lips, comprising, in a physiologicallyacceptable medium containing at least one oil other than isododecane ordecamethylcyclopentasiloxane, preferably a non-volatile oil and inparticular a silicone oil, at least one supramolecular polymer asdefined above and at least one block ethylenic polymer.

A composition intended for caring for and/or making up the lips,especially of lipstick type, comprising, in a physiologically acceptablemedium, at least one supramolecular polymer as defined above, and atleast one block ethylenic polymer, is also considered according to theinvention.

The present also invention relates to a composition for making up and/orcaring for the skin and/or the lips, comprising, in a physiologicallyacceptable medium, at least one supramolecular polymer as defined aboveand more than 5% by weight or even at least 6% by weight of siliconeresin(s) relative to its total weight.

In particular, the present invention relates to a composition for makingup and/or caring for the skin and/or the lips, comprising, in aphysiologically acceptable medium, at least one supramolecular polymeras defined above, at least one silicone resin and at least 1% by weightof organic or inorganic fillers(s).

The present invention also relates to a composition for making up and/orcaring for the skin and/or the lips, comprising, in a physiologicallyacceptable medium, at least one supramolecular polymer as defined above,at least one silicone resin and at least one pigment other than a nacre.

The present invention also relates to a composition for making up and/orcaring for the skin and/or the lips, comprising, in a physiologicallyacceptable medium containing at least one oil other than isododecane ordecamethylcyclopentasiloxane, preferably a non-volatile oil and inparticular at least one silicone oil, at least one supramolecularpolymer as defined above and at least one silicone resin.

The present invention also relates to a composition for making up and/orcaring for the skin and/or the lips, comprising, in a physiologicallyacceptable medium containing less than 4.5% by weight of ethanol, inparticular less than 2% by weight of ethanol and better still less than1% by weight of ethanol, at least one supramolecular polymer as definedabove and at least one silicone resin.

A composition intended for caring for and/or making up the lips,especially of lipstick type, comprising, in a physiologically acceptablemedium, at least one supramolecular polymer as defined above, and atleast one silicone resin, is also considered according to the invention.

The compositions under consideration according to the invention may bein solid or liquid form at 20° C.

For the purposes of the invention, the term “solid” characterizes thestate of the composition at a temperature of 20° C. In particular, asolid composition according to the invention has, at a temperature of20° C. and at atmospheric pressure (760 mmHg), a hardness of greaterthan 30 Nm⁻¹ and preferably greater than 40 Nm⁻¹.

Protocol for Measuring the Hardness:

The hardness of a solid composition especially of lipstick wand type ismeasured according to the following protocol:

The lipstick wand is stored at 20° C. for 24 hours before measuring thehardness.

The hardness may be measured at 20° C. via the “cheese wire” method,which consists in transversely cutting a wand of product, which ispreferably a circular cylinder, by means of a rigid tungsten wire 250 μmin diameter, by moving the wire relative to the stick at a speed of 100mm/minute.

The hardness of the samples of compositions of the invention, expressedin Nm⁻¹, is measured using a DFGS2 tensile testing machine from thecompany Indelco-Chatillon.

The measurement is repeated three times and then averaged. The averageof the three values read using the tensile testing machine mentionedabove, noted Y, is given in grams. This average is converted intonewtons and then divided by L which represents the longest dimensionthrough which the wire passes. In the case of a cylindrical wand, L isequal to the diameter (in metres).

The hardness is converted into Nm^(I) by the equation below:

(Y×10⁻³×9.8)/L

For a measurement at a different temperature, the stick is stored for 24hours at this new temperature before the measurement.

According to this measuring method, a solid composition according to theinvention has a hardness at 20° C. of greater than or equal to 30 Nm⁻¹,preferably greater than 40 Nm⁻¹ and preferably greater than 50 Nm⁻¹.

Preferably, the composition according to the invention especially has ahardness at 20° C. of less than 500 Nm⁻¹, especially less than 400 Nm⁻¹and preferably less than 300.

In particular, a composition whose hardness is greater than 30 Nm⁻¹ issaid to be “solid” at 20° C. and at atmospheric pressure (760 mmHg).

It may also be, in particular in the case of a composition intended forcaring for and/or making up the skin, especially of foundation type, aloose or compact powder or a liquid formulation that may be anhydrous orof the oil-in-water or water-in-oil emulsion type.

Thus, a composition according to the invention may also comprise atleast one supramolecular polymer as defined above, at least onehydrophobic film-forming polymer, and at least 5% by weight of water oreven at least 10% by weight of water relative to its total weight.

Advantageously, the compositions according to the invention areanhydrous.

A composition according to the invention may be in the form of a skinand/or lip makeup composition, especially for facial or bodily skin; itmay be a complexion product such as a foundation, a face powder or aneyeshadow; a lip product such as a lipstick or a lipcare product; aconcealer product; a blusher; an eyeliner; a lip pencil or an eyepencil; a body makeup product; a gloss (lip gloss).

According to a first advantageous embodiment of the invention, thecomposition according to the invention is intended for making up theskin and it is then more particularly a foundation, a face powder, aneyeshadow or a body makeup product.

According to a second advantageous embodiment of the invention, thecomposition according to the invention is intended for making up thelips and it is then more particularly a lipstick (lipstick wand) or agloss (liquid lipstick).

Supramolecular Polymer

The cosmetic compositions according to the invention thus comprise apolyalkene-based (i.e. polyolefin) supramolecular polymer.

For the purposes of the present invention, the term “polyalkene-basedsupramolecular polymer” means a polymer derived from the reaction,especially the condensation, of at least one polyalkene polymerfunctionalized with at least one reactive group, with at least onejunction group functionalized with at least one reactive group capableof reacting with the reactive group(s) of the functionalized polyalkenepolymer, the said junction group being capable of forming at least threeH (hydrogen) bonds and preferably at least four H bonds, preferentiallyfour H bonds.

The term “polyalkene” or “polyolefin” means a polymer derived from thepolymerization of at least one monomer of alkene type, comprising anethylenic unsaturation, the said monomer possibly being pendent or inthe main chain of the said polymer. The term “polyalkene” or“polyolefin” is thus directed towards polymers that may or may notcomprise a double bond. Preferably, the supramolecular polymers usedaccording to the invention are prepared from a polymer derived from thepolymerization of an alkene comprising at least two ethylenicunsaturations.

The supramolecular polymer according to the invention is capable offorming a supramolecular polymer chain or network, by (self)assembly ofsaid polymer according to the invention with at least one otheridentical or different polymer according to the invention, each assemblyinvolving at least one pair of paired junction groups, which may beidentical or different, borne by each of the polymers according to theinvention.

For the purposes of the invention, the teen “junction group” means anygroup comprising groups that donate or accept H bonds, and capable offorming at least three H bonds and preferably at least four H bonds,preferentially four H bonds, with an identical or different partnerjunction group. These junction groups may be lateral to the polymerbackbone (side branching) and/or borne by the ends of the polymerbackbone, and/or in the chain forming the polymer backbone. They may bedistributed in a random or controlled manner.

Functionalized Polyalkene

The polyalkene polymers are functionalized with at least one reactivegroup and preferably with at least two reactive groups. Thefunctionalization preferably occurs at the chain ends. They are thenreferred to as telechelic polymers.

The functionalization groups, or reactive groups, may be attached to thepolyalkene polymer via linkers, preferably linear or branched C₁-C₄alkylene groups, or directly via a single bond.

Preferably, the functionalized polyalkene polymers have a number-averagemolecular mass (Mn) of between 1000 and 8000.

Even more preferably, they have a number-average molecular mass ofbetween 1000 and 5000, or even between 1500 and 4500.

Even more preferably, they have a number-average molecular mass ofbetween 2000 and 4000.

Preferably, the functionalized polyalkene polymer, capable of formingall or part of the polymer backbone of the supramolecular polymeraccording to the invention (preferably, it forms all of the backbone ofthe polymer), is of formula HO—P—OH in which:

-   -   P represents a homo- or copolymer that may be obtained by        polymerization of one or more linear, cyclic and/or branched,        polyunsaturated (preferably diunsaturated) C₂-C₁₀ and preferably        C₂-C₄ alkenes,

P preferably represents a homo- or copolymer that may be obtained bypolymerization of one or more linear, cyclic and/or branched, C₂-C₄diunsaturated alkenes.

More preferably, P represents a polymer chosen from a polybutylene, apolybutadiene (such as a 1,4-polybutadiene or a 1,2-polybutadiene), apolyisoprene, a poly(1,3-pentadiene) and a polyisobutylene, andcopolymers thereof.

According to one preferred embodiment, P represents apoly(ethylene/butylene) copolymer.

The preferred poly(ethylene/butylenes) are copolymers of 1-butene and ofethylene. They may be represented schematically by the followingsequence of units:

[—CH₂—CH₂-] and [—CH₂CH(CH₂—CH₃)—]

According to a second preferred embodiment, P is a polybutadienehomopolymer, preferably chosen from a 1,4-polybutadiene or a1,2-polybutadiene. The polybutadienes may be 1,4-polybutadienes or1,2-polybutadienes, which may be represented schematically,respectively, by the following sequences of units:

[—CH₂—CH═CH—CH₂-](1,4-polybutadienes)

[—CH₂—CH(CH═CH₂)—](1,2-polybutadienes)

Preferably, they are 1,2-polybutadienes. Preferably, P is a1,2-polybutadiene homopolymer.

According to another embodiment, P is a polyisoprene. Polyisoprenes maybe represented schematically by the following sequences of units:

A mixture of above units may obviously also be used, so as to formcopolymers.

The functionalized polyalkene polymers may be totally hydrogenated toavoid the risks of crosslinking Preferably, the functionalizedpolyalkene polymers used in the compositions according to the inventionare hydrogenated.

Preferably, the polyalkene polymers are hydrogenated and functionalizedwith at least two OH reactive groups, preferably at the ends of thepolymers.

Preferably, they have functionality as hydroxyl end groups of from 1.8to 3 and preferably in the region of 2.

Polydienes containing hydroxyl end groups are especially defined, forexample, in FR 2 782 723. They may be chosen from polybutadiene,polyisoprene and poly(1,3-pentadiene) homopolymers and copolymers.Mention will be made in particular of the hydroxylated polybutadienessold by the company Sartomer, for instance the Krasol® Resins and thePoly be Resins. Preferably, they are dihydroxylated hydrogenated1,2-polybutadiene homopolymers, such as the range Nisso-PB 1, GI3000,GI2000 and GI1000 sold by the company Nisso, which may be representedschematically by the following formula:

Preferably, n is between 14 and 105 and preferably between 20 and 85.

These polymers have the following number-average molecular masses:G13000 of Mn=4700, GI2000 of Mn=3300 and GI1000 of Mn=1500. These valueswere measured by GPC according to the following protocol:

Protocol for Determining the Molecular Masses of the SupramolecularPolymer by GPC

Determination of the number-average molecular mass Mn, theweight-average molecular mass and Mw the polydispersity index Mw/ Mn inpolystyrene equivalents.

Preparation of the Standard Solutions

Prepare the polystyrene standards from Varian kits (ref.: PS-H(PL2010-0200)

The masses of the standards are as follows:

-   -   PS 6035000-PS 3053000-PS 915000-PS 483000-PS 184900-PS 60450-PS        19720 PS 8450-PS 3370 PS 1260-PS 580

Inject 100 μl of each of the solutions into the calibration column.

Preparation of the Sample:

Prepare a solution with a solids content of 0.5% in THF.

Prepare the solution about 24 hours before injection.

Filter the solution through a Millex FH filter (0.45 μm).

Inject into the column.

Chromatographic Conditions:

Columns: PL Rapid M (batch 5M-Poly-008-15) from Polymer Labs

-   -   PL-gel HTS-D (batch 5M-MD-72-2) from Polymer Labs    -   PL-gel HTS-F (10M-2-169B-25) from Polymer Labs    -   PL-Rapid-F (6M-0L1-011-6) from Polymer Labs    -   Length: 150 mm—inside diameter: 7.5 mm        Pump: isocratic M1515 Waters

Eluent: THF

-   -   Flow rate: 1 ml/minute    -   Temperature: ambient        Injection: 100 μl at 0.5% AM in the eluent        Detection: RI 64 mV (Waters 2424 refractometer) Temperature: 45°        C.    -   UV at 254 nm at 0.1 OD (Waters 2487 UV detector)        Integrator: Empower option GPC

Determination of the Molar Masses

The average molar masses are determined by plotting the calibrationcurve: log Molar mass=f (elution volume at the top of the RI detectionpeak) and using the software Empower option GPC from Waters.

Among the polyolefins with hydroxyl end groups, mention may be madepreferentially of polyolefins, homopolymers or copolymers withα,ω-hydroxyl end groups, such as polyisobutylenes with α,ω-hydroxyl endgroups; and the copolymers of formula:

especially those sold by Mitsubishi under the brand name Polytail.

Junction Group

The supramolecular polymers according to the invention also have intheir structure at least one residue of a junction group capable offorming at least three H bonds and preferably at least four H bonds, thesaid junction group being initially functionalized with at least onereactive group.

Unless otherwise mentioned, the term “junction group” means in thepresent description the group without its reactive function.

The reactive groups are attached to the junction group via linkers L.

L is a single bond or a saturated or unsaturated C₁₋₂₀ divalentcarbon-based group chosen in particular from a linear or branched C₁-C₂₀alkylene; a C₅-C₂₀ (alkyl)cycloalkylene alkylene (preferablycyclohexylene methylene), a C₁₁-C₂₀ alkylene-biscycloalkylene(preferably alkylene-biscyclohexylene), a C₆-C₂₀ (alkyl)arylene, analkylene-bisarylene (preferably an alkylene-biphenylene), the linker Lpossibly being substituted with at least one alkyl group and/or possiblycomprising 1 to 4 N and/or O heteroatoms, especially in the form of anNO₂ substituent.

Preferably, the linker is a group chosen form phenylene;1,4-nitrophenylene; 1,2-ethylene; 1,6-hexylene; 1,4-butylene;1,6-(2,4,4-trimethylhexylene); methylpentylene); 1,5-(5-methylhexylene);1,6-(6-methylheptylene); 1,5-(2,2,5-trimethylhexylene);1,7-(3,7-dimethyloctylene); -isophorone-; 4,4′-methylenebis(cyclohexylene); tolylene; 2-methyl-1,3-phenylene;4-methyl-1,3-phenylene; 4,4-biphenylenemethylene;

Preferably, the linker is chosen from the groups:

-   -   C₅-C₂₀ (alkyl)cycloalkylene alkylene, such as isophorone,    -   C₁₁-C₂₅ alkylene-biscycloalkylene, such as 4,4′-methylene        biscyclohexene,    -   C₁-C₂₀ alkylene, such as —(CH₂)₂—; —(CH₂)₆—;        —CH₂CH(CH₃)—CH₂—C(CH₃)₂—CH₂—CH₂, and    -   C₆-C₂₀ (alkyl) phenylene, such as 2-methyl-1,3-phenylene.

Preferably, L is chosen from: -isophorone-; —(CH₂)₂—; —(CH₂)₆—;CH₂CH(CH₃)—CH₂—C(CH₃)₂—CH₂—CH₂; 4,4′-methylene biscyclohexylene;2-methyl-1,3-phenylene.

According to one particularly preferred embodiment, the linker is analkylcycloalkylene alkylene.

Preferably, according to this embodiment, the linker is an isophoronegroup.

The term “isophorone” means the following group:

The said reactive groups functionalizing the junction group must becapable of reacting with the —OH reactive group(s) borne by thefunctionalized polyalkene.

Reactive groups that may be mentioned include isocyanate (—N═C═O) andthioisocyanate (—N═C═S) groups. Preferably, it is a group —N═C═O(isocyanate).

The functionalized junction groups capable of forming at least three Hbonds may comprise at least three identical or different functionalgroups, and preferably at least four functional groups, chosen from:

These functional groups may be classified into two categories:

-   -   functional groups that donate H bonds:

-   -   functional groups that accept H bonds:

The junction groups capable of forming at least three H bonds form abasic structural element comprising at least three groups, preferably atleast four groups and more preferentially four functional groups capableof establishing H bonds. The said basic structural elements capable ofestablishing H bonds may be represented schematically in the followingmanner:

in which X_(i) is an H-bond accepting functional group (identical ordifferent) and Y_(i) is an H-bond donating functional group (identicalor different).

Thus, each structural element should be capable of establishing H bondswith one or more partner structural elements, which are identical (i.e.self-complementary) or different, such that each pairing of two partnerstructural elements takes place by formation of at least three H bondsand preferably at least four H bonds, more preferentially four H bonds.

A proton acceptor X will pair with a proton donor Y. Severalpossibilities are thus offered, for example pairing of

XXXX with YYYY;

XXXY with YYYX;

XXYX with YYXY;

XYYX with YXXY;

XXYY with YYXX self-complementary or otherwise;

XYXY with YXYX self-complementary or otherwise.

Preferably, the junction groups may establish four H bonds with anidentical (or self-complementary) partner group among which are twodonor bonds (for example NH) and two acceptor bonds (for example CO and—C═N—).

Preferably, the junction groups capable of forming at least four H bondsare chosen from:

the ureidopyrimidones of formula:

it being understood that all the tautomeric forms are included.

In this formula, the radicals have the following meanings:

-   -   the radicals R₁ (or the radicals R₁ and R₂) are single bonds        constituting the point of attachment of the junction group to        the linker capable of forming at least three H bonds (preferably        four H bonds) on the rest of the graft. Preferably, the said        point of attachment is borne solely by R₁, which is a single        bond.    -   the radical R₂ represents a divalent group chosen from a single        bond or a C₁-C₆ alkylene or a monovalent group chosen from a        single bond, a hydrogen atom or a linear or branched C₁-C₁₀        saturated monovalent hydrocarbon-based group, which may contain        one or more heteroatoms such as O, S or N, these groups being        optionally substituted with a hydroxyl, amino and/or thio        function.

Preferably, the radical R2 may be a single bond or a monovalent groupchosen from H, CH₂OH and (CH₂)₂—OH, CH₃.

According to one particularly preferred embodiment, R₂ is H.

-   -   the radical R₃ represents a monovalent or divalent group, in        particular, R₃ is chosen from a hydrogen atom or a linear or        branched C₁-C₁₀ saturated monovalent hydrocarbon-based group,        which may contain one or more heteroatoms such as 0, S or N,        these groups being optionally substituted with a hydroxyl, amino        and/or thio function.

Preferably, the radical R₃ may be a monovalent group chosen from H,CH₂OH and (CH₂)₂—OH, CH₃.

According to one particularly preferred embodiment, R₃ is a methylgroup.

According to one preferred embodiment, the junction groups are chosenfrom 2-ureidopyrimidone and 6-methyl-2-ureidopyrimidone.

Preferably, the preferred junction group is 6-methyl-2-ureidopyrimidone.

The junction groups, and especially the ureidopyrimidone junctiongroups, may be added directly or may be formed in situ during theprocess for preparing the supramolecular polymer. The first and secondpreparation methods described below illustrate these two alternatives,respectively.

In particular, the functionalized junction groups capable of reactingwith the functionalized polyalkene polymer to give the supramolecularpolymer according to the invention are preferably of formula:

in which L is as defined above.

Preferably, L is chosen from the groups:

-   -   C₅-C₂₀ (alkyl)cycloalkylene alkylene, such as isophorone,    -   C₁₁-C₂₅ alkylene-biscycloalkylene, such as 4,4′-methylene        biscyclohexene,    -   C₁-C₂₀ alkylene, such as —(CH₂)₂—; —(CH₂)₆—;        —CH₂CH(CH₃)—CH₂—C(CH₃)₂—CH₂—CH₂, and    -   C₆-C₂₀ (alkyl) phenylene, such as 2-methyl-1,3-phenylene.

Preferably, L is chosen from: -isophorone-; —(CH₂)₆—; 4,4′-methylenebiscyclohexylene.

According to one particularly preferred embodiment, the junction groupis of formula

in which L is isophorone.

In one particularly preferred embodiment, the supramolecular polymer ofthe invention corresponds to the formula:

in which:

-   -   L′ and L″ have, independently of each other, the meaning given        above for L;    -   X, X′=O and P has the meaning given above for the functionalized        polyalkene polymer.

Preferably, L′ and L″ represent a saturated or unsaturated C₁-C₂₀divalent carbon-based group, chosen in particular from a linear orbranched C₁-C₂₀ alkylene; a C₅-C₂₀ (alkyl)cycloalkylene, analkylene-biscycloalkylene and a C₆-C₂₀ (alkyl)arylene. Preferably, L′and L″ represent an -isophorone-; —(CH₂)₂—; —(CH₂)₆—;CH₂CH(CH₃)—CH₂—C(CH₃)₂—CH₂—CH₂; 4,4′-methylene biscyclohexylene;2-methyl-1,3-phenylene group.

Preferably, L′ and L″ are identical.

Preferably, L′ and L″ are an isophorone group.

Preferably, P is hydrogenated and represents a polyethylene, apolybutylene, a polybutadiene, a polyisoprene, a poly(1,3-pentadiene), apolyisobutylene, or a copolymer thereof, especially apoly(ethylene/butylene).

Preferably, P is a hydrogenated polybutadiene, preferably a hydrogenated1,2-polybutadiene.

In one particularly preferred embodiment, the supramolecular polymer ofthe invention corresponds to the formula:

Preparation Process

The polymer according to the invention may be prepared via the processesusually used by a person skilled in the art, especially for forming aurethane bond between the free OH functions of a polyalkene, and theisocyanate functions borne by the junction group.

By way of non-limiting illustration, a first general preparation processconsists in:

-   -   optionally ensuring that the polymer to be functionalized does        not comprise any residual water,    -   heating the said polymer comprising at least two OH reactive        functions to a temperature that may be between 60° C. and 140°        C.; the hydroxyl number of the polymer being able to serve as        reference in order to measure the degree of progress of the        reaction;    -   adding, preferably directly, the ureidopyrimidone junction group        bearing the reactive functions, especially isocyanate such as        those described in patent WO 2005/042 641; especially such as        the compounds of CAS NUMBER=32093-85-9 and 709028-42-2,    -   optionally stirring the mixture, under a controlled atmosphere,        at a temperature of about 90-130° C.; for 1 to 24 hours;    -   optionally monitoring by infrared spectroscopy the disappearance        of the characteristic isocyanate band (between 2500 and 2800        cm⁻¹) so as to stop the reaction on total disappearance of the        peak, and then allowing the final product to cool to room        temperature.

The reaction may also be monitored by assaying the hydroxyl functions;it is also possible to add ethanol in order to ensure totaldisappearance of the residual isocyanate functions.

The reaction may be performed in the presence of a solvent, especiallymethyltetrahydrofuran, tetrahydrofuran, toluene, propylene carbonate orbutyl acetate. It is also possible to add a conventional catalyst forforming a urethane bond. An example that may be mentioned is dibutyltindilaurate. The polymer may finally be washed and dried, or evenpurified, according to the general knowledge of a person skilled in theart.

According to the second preferred mode of preparation, the reaction maycomprise the following steps:

(i) functionalization of the polymer, which has preferably been driedbeforehand, with a diisocyanate according to the reaction scheme:

OH-polymer-OH(1 eq.)+NCO—X—NCO(1eq.)→OCN—X—NH—(O)CO-polymer-OC(O)—NH—X—NCO

The diisocyanate may optionally be in excess relative to the polymer.This first step may be performed in the presence of solvent, at atemperature of between 20° C. and 100° C. This first step may befollowed by a period of stirring under a controlled atmosphere for 1 to24 hours. The mixture may optionally be heated. The degree of progressof this first step may be monitored by assaying the hydroxyl functions;

and then

(ii) reaction of the prepolymer obtained above with 6-methylisocytosineof formula:

this second step may optionally be performed in the presence of acosolvent such as toluene, butyl acetate or propylene carbonate. Thereaction mixture may be heated to between 80° C. and 140° C. for a timeranging between 1 and 24 hours. The presence of a catalyst, especiallydibutyltin dilaurate, may promote the production of the desired finalproduct.

The reaction may be monitored by infrared spectroscopy, by monitoringthe disappearance of the characteristic peak of isocyanate between 2200and 2300 cm⁻¹. At the end of the reaction, ethanol may be added to thereaction medium in order to neutralize any residual isocyanatefunctions. The reaction mixture may be optionally filtered. The polymermay also be stripped directly in a cosmetic solvent.

According to one particular mode, the said supramolecular polymer isdissolved in a hydrocarbon-based oil, which is preferably volatile, inparticular isododecane.

Thus, the composition of the invention will comprise at least onehydrocarbon-based oil, which is preferably volatile, in particular atleast isododecane, especially provided by the supramolecular polymersolution.

In particular, the supramolecular polymer(s) may be present in acomposition according to the invention in an amount ranging from 0.1% to60% by weight of solids, relative to the total weight of thecomposition.

According to one preferred variant, the supramolecular polymer(s) may bepresent in a composition according to the invention in an amount rangingfrom 0.2% to 50% by weight, relative to the total weight of thecomposition.

According to an even more preferred variant, the supramolecularpolymer(s) may be present in a composition according to the invention inan amount ranging from 0.3% to 40% by weight, relative to the totalweight of the composition.

According to an even more preferred variant, the supramolecularpolymer(s) may be present in a composition according to the invention inan amount ranging from 0.5% to 30% by weight, relative to the totalweight of the composition.

According to one particular mode, these contents are used for acomposition in the form of a composition for caring for and/or making upthe skin, especially of the face, in particular a foundation.

In one particular embodiment of the invention, a composition is in theform of a composition for caring for and/or making up the skin,especially of the face (e.g.: a foundation) and the supramolecularpolymer(s) may be present therein in a content ranging from 2.5% to 60%by weight of solids relative to the total weight of the composition.

According to an even more preferred variant, a composition is in theform of a composition for caring for and/or making up the skin,especially of the face (e.g.: a foundation) and the supramolecularpolymer(s) may be present therein in a content ranging from 2.5% to 40%by weight of solids relative to the total weight of the composition.

According to an even more preferred variant, a composition is in theform of a composition for caring for and/or making up the skin,especially of the face (e.g.: a foundation) and the supramolecularpolymer(s) may be present therein in a content ranging from 3% to 30% byweight of solids relative to the total weight of the composition.

In another particular embodiment of the invention, a composition is inthe form of a composition for caring for and/or making up the lips(e.g.: a lipstick) and the supramolecular polymer(s) may be presenttherein in a content ranging from 0.1% to 60% by weight of solidsrelative to the total weight of the composition.

According to one preferred variant, a composition is in the form of acomposition for caring for and/or making up the lips (e.g.: a lipstick)and the supramolecular polymer(s) may be present therein in a contentranging from 0.2% to 40% by weight of solids relative to the totalweight of the composition.

According to an even more preferred variant, a composition is in theform of a composition for caring for and/or making up the lips (e.g.: alipstick) and the supramolecular polymer(s) may be present therein in acontent ranging from 0.5% to 30% by weight of solids relative to thetotal weight of the composition.

Advantageously, a composition according to the invention, in particularin the case of a composition for making up the skin and/or the lips,comprises a content of supramolecular polymer of between 5% and 99% byweight relative to the weight of the composition excluding volatilecompound(s) (in particular relative to the weight of the compositionexcluding volatile oil(s), such as isododecane, for example).

This content reflects the resulting content of supramolecular polymer(s)in a deposit made with a composition or according to the process of theinvention, especially on keratin materials such as the skin and/or lips,for example, after evaporation of the volatile compounds.

Preferably, the composition according to the invention, in particular inthe case of a makeup composition, comprises a content of supramolecularpolymer of between 10% and 90% by weight relative to the weight of thecomposition excluding volatile compound(s), preferably between 15% and80%.

Hydrophobic Film-Forming Polymers

For the purposes of the invention, the term “polymer” means a compoundcorresponding to the repetition of one or more units (these units beingderived from compounds known as monomers). This or these units(s) arerepeated at least twice and preferably at least three times.

For the purposes of the present invention, the term “hydrophobicfilm-forming polymer” is intended to denote a film-forming polymer thathas no affinity for water and, in this respect, does not lend itself toformulation in the form of a solute in an aqueous medium. In particular,the term “hydrophobic polymer” means a polymer with a solubility inwater at 25° C. of less than 1% by weight.

The term “film-forming polymer” means a polymer that is capable offorming, by itself or in the presence of an auxiliary film-formingagent, a macroscopically continuous film that adheres to a support,especially to keratin materials, preferably a cohesive film, and betterstill a film whose cohesion and mechanical properties are such that thesaid film may be isolable and manipulable in isolation, for example whenthe said film is prepared by pouring onto a non-stick surface, forinstance a Teflon-coated or silicone-coated surface.

In one preferred embodiment, the hydrophobic film-forming polymer is apolymer chosen from the group comprising:

-   -   film-forming polymers that are soluble in an organic solvent        medium, in particular liposoluble polymers; this means that the        polymer is soluble or miscible in the organic medium and will        form a single homogeneous phase when it is incorporated into the        medium,    -   film-forming polymers that are dispersible in an organic solvent        medium; this means that the polymer forms an insoluble phase in        the organic medium, the polymer remaining stable and/or        compatible once incorporated into this medium. In particular,        such polymers may be in the form of non-aqueous dispersions of        polymer particles, preferably dispersions in silicone-based or        hydrocarbon-based oils; in one embodiment, the non-aqueous        dispersions of polymer comprise polymer particles stabilized on        their surface with at least one stabilizer; these non-aqueous        dispersions are often referred to as “NADs”,    -   film-forming polymers in the form of aqueous dispersions of        polymer particles; this means that the polymer forms an        insoluble phase in water, the polymer remaining stable and/or        compatible once incorporated into the water, the polymer        particles possibly being stabilized at their surface with at        least one stabilizer. These polymer particles are often referred        to as “latices”; in this case, the composition must comprise an        aqueous phase.

Hydrophobic film-forming polymers that may especially be mentionedinclude homopolymers and copolymers of a compound containing anethylenic unit, acrylic polymers and copolymers, polyurethanes,polyesters, polyureas, cellulose-based polymers, for instancenitrocellulose, silicone polymers such as silicone resins, siliconepolyamides, polymers with a non-silicone organic backbone grafted withmonomers containing a polysiloxane, polyamide polymers and copolymers,and polyisoprenes.

A cosmetic makeup composition according to the invention may comprisefrom 0.1% to 30%, preferably from 0.2% to 20% by weight and even morepreferentially from 0.5% to 15% by weight of hydrophobic film-formingpolymer(s).

Advantageously, the polymer according to the invention and thehydrophobic film-forming polymer are used in a polymer(s)/hydrophobicfilm-forming polymer(s) weight ratio ranging from 1 to 30 and moreparticularly from 1.5 to 10.

As hydrophobic film-forming polymers that are most particularly suitablefor use in the invention, mention may be made especially of:

-   -   polyamide silicone block polymers,    -   block ethylenic polymers,    -   vinyl polymers comprising at least one carbosiloxane dendrimer        derivative,    -   copolymers comprising carboxylate groups and        polydimethylsiloxane groups,    -   silicone resins (T resin, MQ resin),    -   lipodispersible polymers in the form of non-aqueous dispersions        of polymer particles,    -   and mixtures thereof.

Silicone Resins

According to one embodiment variant, a composition according to theinvention may comprise, as hydrophobic film-forming polymer, at leastone silicone resin.

More generally, the term “resin” means a compound whose structure isthree-dimensional. “Silicone resins” are also known as “silicone-basedresins” or “siloxane resins”. Thus, for the purposes of the presentinvention, a polydimethylsiloxane is not a silicone resin.

The nomenclature of silicone resins (also known as siloxane resins) isknown under the name “MDTQ”, the resin being described as a function ofthe various siloxane monomer units that it comprises, each of theletters “MDTQ” characterizing a type of unit.

The letter “M” represents the Monofunctional unit of formulaR1R2R3SiO_(1/2), the silicon atom being connected to only one oxygenatom in the polymer comprising this unit.

The letter “D” means a Difunctional unit R1R2SiO_(2/2) in which thesilicon atom is connected to two oxygen atoms.

The letter “T” represents a Trifunctional unit of formula R1 SiO_(3/2).

Such resins are described, for example, in the “Encyclopaedia of PolymerScience and Engineering, vol. 15, John Wiley & Sons, New York (1989),pp. 265-270 and U.S. Pat. No. 2,676,182, U.S. Pat. No. 3,627,851, U.S.Pat. No. 3,772,247 and U.S. Pat. No. 5,248,739 or alternatively U.S.Pat. No. 5,082,706, U.S. Pat. No. 5,319,040, U.S. Pat. No. 5,302,685 andU.S. Pat. No. 4,935,484.

In the M, D and T units defined previously, R, i.e. R₁ and R₂,represents a hydrocarbon-based radical (especially alkyl) containingfrom 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or ahydroxyl group.

Finally, the letter “Q” means a tetrafunctional unit SiO_(4/2) in whichthe silicon atom is linked to four oxygen atoms, which are themselveslinked to the rest of the polymer.

Various silicone resins with different properties may be obtained fromthese different units, the properties of these polymers varying as afunction of the type of monomer (or unit), the nature and number of theradical R, the length of the polymer chain, the degree of branching andthe size of the pendent chains.

As silicone resins that may be used in the compositions according to theinvention, use may be made, for example, of silicone resins of MQ type,of T type or of MQT type.

MQ resins:

As examples of silicone resins of MQ type, mention may be made of thealkyl siloxysilicates of formula [(R1)₃SiO_(1/2)]_(x)(SiO_(4/2))_(y) (MQunits) in which x and y are integers ranging from 50 to 80, and suchthat the group R1 represents a radical as defined previously, and ispreferably an alkyl group containing from 1 to 8 carbon atoms,preferably a methyl group.

-   -   As examples of solid silicone resins of MQ type of trimethyl        siloxysilicate type, mention may be made of those sold under the        reference SR1000 by the company General Electric, under the        reference TMS 803 by the company Wacker, or under the name        KF-7312J by the company Shin-Etsu or DC749 or DC593 by the        company Dow Corning.    -   As silicone resins comprising MQ siloxysilicate units, mention        may also be made of phenylalkylsiloxysilicate resins, such as        phenylpropyldimethylsiloxysilicate (Silshine 151 sold by the        company General Electric). The preparation of such resins is        described especially in patent U.S. Pat. No. 5,817,302.

Resins T:

Examples of these silicone resins of type T that may be mentionedinclude the polysilsesquioxanes of formula (RSiO₃₂)_(x) (units T) inwhich x is greater than 100 and such that the group R is an alkyl groupcontaining from 1 to 10 carbon atoms, the said polysilsesquioxanes alsopossibly comprising Si—OH end groups.

Polymethylsilsesquioxane resins that may preferably be used are those inwhich R represents a methyl group, for instance those sold:

-   -   by the company Wacker under the reference Resin MK, such as        Belsil PMS MK: polymer comprising CH₃SiO_(3/2) repeating units        (units T), which may also comprise up to 1% by weight of        (CH₃)₂SiO_(2/2) units (units D) and having an average molecular        weight of about 10 000 g/mol, or    -   by the company Shin-Etsu under the reference KR-220L, which are        composed of units T of formula CH₃SiO_(3/2) and have Si—OH        (silanol) end groups, under the reference KR-242A, which        comprise 98% of units T and 2% of dimethyl units D and have        Si—OH end groups, or alternatively under the reference KR-251        comprising 88% of units T and 12% of dimethyl units D and have        Si—OH end groups.

MQT Resins:

Resins comprising MQT units that are especially known are thosementioned in document U.S. Pat. No. 5,110,890.

A preferred form of resins of MQT type are MQT-propyl (also known asMQTPr) resins. Such resins that may be used in the compositionsaccording to the invention are especially the resins described andprepared in patent application WO 2005/075 542, the content of which isincorporated herein by reference.

The MQ-T-propyl resin preferably comprises the following units:

(R1₃SiO_(1/2))_(a)  (i)

(R2₂SiO_(2/2))_(b)  (ii)

(R3SiO_(3/2))_(c) and  (iii)

(SiO_(4/2))_(d)  (iv)

with

R1, R2 and R3 independently representing a hydrocarbon-based radical(especially alkyl) containing from 1 to 10 carbon atoms, a phenyl group,a phenylalkyl group or a hydroxyl group, and preferably an alkyl radicalcontaining from 1 to 8 carbon atoms or a phenyl group,

a being between 0.05 and 0.5,

b being between 0 and 0.3,

c being greater than 0,

d being between 0.05 and 0.6,

a+b+c+d=1, and a, b, c and d being mole fractions,

on condition that more than 40 mol % of the groups R3 of the siloxaneresin are propyl groups.

Preferably, the siloxane resin comprises the following units:

(R1₃SiO_(1/2))_(a)  (i)

(R3SiO_(3/2)), and  (iii)

(SiO_(4/2))_(d)  (iv)

with

R1 and R3 independently representing an alkyl group containing from 1 to8 carbon atoms, R1 preferably being a methyl group and R3 preferablybeing a propyl group,

a being between 0.05 and 0.5 and preferably between 0.15 and 0.4,

c being greater than 0 and preferably between 0.15 and 0.4,

d being between 0.05 and 0.6, preferably between 0.2 and 0.6, oralternatively between 0.2 and 0.55,

a+b+c+d=1 and a, b, c and d being mole fractions,

on condition that more than 40 mol % of the groups R3 of the siloxaneresin are propyl groups.

The siloxane resins that may be used according to the invention may beobtained via a process comprising the reaction of:

A) an MQ resin comprising at least 80 mol % of units (R1₃SiO_(1/2))_(a)and (SiO_(4/2))_(d)

R1 representing an alkyl group containing from 1 to 8 carbon atoms, anaryl group, a carbinol group or an amino group,

a and d being greater than 0,

the ratio aid being between 0.5 and 1.5; and

B) a T-propyl resin comprising at least 80 mol % of units(R3SiO_(3/2))_(c),

R3 representing an alkyl group containing from 1 to 8 carbon atoms, anaryl group, a carbinol group or an amino group,

c being greater than 0,

on condition that at least 40 mol % of the groups R3 are propyl groups,

in which the mass ratio A/B is between 95/5 and 15/85 and the mass ratioA/B is preferably 30/70.

Advantageously, the mass ratio A/B is between 95/5 and 15/85.Preferably, the ratio A/B is less than or equal to 70/30. Thesepreferred ratios have been proven to produce deposits that arecomfortable due to the absence of percolation of the rigid MQ resinparticles in the deposit.

Thus, preferably, the silicone resin is chosen from the groupcomprising:

a) a resin of MQ type, chosen especially from (i) alkyl siloxysilicates,which may be trimethyl siloxysilicates, of formula[(R1)₃SiO_(1/2)]_(x)(SiO_(4/2))_(y), in which x and y are integersranging from 50 to 80, and such that the group R1 represents ahydrocarbon-based radical containing from 1 to 10 carbon atoms, a phenylgroup, a phenylalkyl group or a hydroxyl group, and preferably is analkyl group containing from 1 to 8 carbon atoms, preferably a methylgroup, and (ii) phenylalkyl siloxysilicate resins, such asphenylpropyldimethyl siloxysilicate, and/or

b) a resin of T type, chosen especially from the polysilsesquioxanes offormula (RSiO_(3/2))_(x), in which x is greater than 100 and the group Ris an alkyl group containing from 1 to 10 carbon atoms, for example amethyl group, the said polysilsesquioxanes also possibly comprisingSi—OH end groups, and/or

-   -   c) a resin of MQT type, especially of MQT-propyl type, which may        comprise units (i) (R1₃SiO_(1/2))_(a), (ii)        (R2₂SiO_(2/2))_(b), (iii) (R3SiO_(3/2))_(c) and (iv)        (SiO_(4/2))_(d),

with R1, R2 and R3 independently representing a hydrocarbon-basedradical, especially alkyl, containing from 1 to 10 carbon atoms, aphenyl group, a phenylalkyl group or a hydroxyl group and preferably analkyl radical containing from 1 to 8 carbon atoms or a phenyl group,

a being between 0.05 and 0.5,

b being between 0 and 0.3,

c being greater than 0,

d being between 0.05 and 0.6,

a+b+c+d=1, and a, b, c and d being mole fractions,

on condition that more than 40 mol % of the groups R3 of the siloxaneresin are propyl groups.

Lipodispersible Film-Forming Polymers in the Form of Non-AqueousDispersions of Polymer Particles, Also Known as NADs

According to another embodiment variant, a composition according to theinvention may comprise, as hydrophobic film-forming polymer, at leastone polymer chosen from lipodispersible film-forming polymers in theform of non-aqueous dispersions of polymer particles, also known asNADs.

Non-aqueous dispersions of hydrophobic film-forming polymer that may beused include dispersions of particles of a grafted ethylenic polymer,preferably an acrylic polymer, in a liquid oily phase:

-   -   either in the form of ethylenic polymer particles dispersed in        the absence of additional stabilizer at the surface of the        particles, as described especially in document WO 04/055 081,    -   or in the form of surface-stabilized particles dispersed in the        liquid fatty phase. The dispersion of surface-stabilized polymer        particles may be manufactured as described in document        EP-A-749 747. The polymer particles may in particular be        surface-stabilized by means of a stabilizer that may be a block        polymer, a grafted polymer and/or a random polymer, alone or as        a mixture. Dispersions of film-forming polymer in the liquid        fatty phase, in the presence of stabilizers, are especially        described in documents EP-A-748 746, EP-A-923 928 and EP-A-930        060, the content of which is incorporated by reference into the        present patent application.

Advantageously, dispersions of ethylenic polymer particles dispersed inthe absence of additional stabilizer at the surface of the saidparticles are used.

Examples of polymers of NAD type that may be mentioned more particularlyinclude acrylic dispersions in isododecane, for instance Mexomer PAP@(acrylic copolymer as a dispersion in isododecane (25%) withpyrene/isoprene copolymer) sold by the company Chimex.

Block Ethylenic Copolymer

According to a first embodiment of the invention, the hydrophobicfilm-forming polymer is a block ethylenic copolymer, containing at leasta first block with a glass transition temperature (Tg) of greater thanor equal to 40° C. and being totally or partly derived from one or morefirst monomers, which are such that the homopolymer prepared from thesemonomers has a glass transition temperature of greater than or equal to40° C., and at least a second block with a glass transition temperatureof less than or equal to 20° C. and being derived totally or partly fromone or more second monomers, which are such that the homopolymerprepared from these monomers has a glass transition temperature of lessthan or equal to 20° C., the said first block and the said second blockbeing connected together via a statistical intermediate segmentcomprising at least one of the said first constituent monomers of thefirst block and at least one of the said second constituent monomers ofthe second block, and the said block copolymer having a polydispersityindex I of greater than 2.

The block polymer used according to the invention thus comprises atleast one first block and at least one second block.

The term “at least one block” means one or more blocks.

The term “block” polymer means a polymer comprising at least twodifferent blocks and preferably at least three different blocks.

The term “ethylenic” polymer means a polymer obtained by polymerizationof ethylenically unsaturated monomers.

The block ethylenic polymer used according to the invention is preparedexclusively from monofunctional monomers.

This means that the block ethylenic polymer used according to thepresent invention does not contain any multifunctional monomers, whichmake it possible to break the linearity of a polymer so as to obtain abranched or even crosslinked polymer, as a function of the content ofmultifunctional monomer. The polymer used according to the inventiondoes not, either, contain any macromonomers (the term “macromonomer”means a monofunctional monomer containing pendent groups of polymericnature, and preferably having a molecular mass of greater than 500g/mol, or alternatively a polymer comprising on only one of its ends apolymerizable (or ethylenically unsaturated) end group), which are usedin the preparation of a grafted polymer.

It is pointed out that, in the text hereinabove and hereinbelow, theterms “first” and “second” blocks do not in any way condition the orderof the said blocks in the structure of the block polymer.

The first block and the second block of the polymer used in theinvention may be advantageously mutually incompatible.

The term “mutually incompatible blocks” means that the mixture formedfrom the polymer corresponding to the first block and form the polymercorresponding to the second block is not miscible in the polymerizationsolvent that is in major amount by weight for the block polymer, at roomtemperature (25° C.) and atmospheric pressure (10⁵ Pa), for a content ofthe mixture of the said polymers of greater than or equal to 5% byweight, relative to the total weight of the mixture of the said polymersand of the said polymerization solvent, it being understood that:

-   -   i) the said polymers are present in the mixture in a content        such that the respective weight ratio ranges from 10/90 to        90/10, and that    -   ii) each of the polymers corresponding to the first and second        blocks has an average (weight-average or number-average)        molecular mass equal to that of the block polymer ±15%.

In the case of a mixture of polymerization solvents, and in the eventthat two or more solvents are present in identical mass proportions, thesaid polymer mixture is immiscible in at least one of them.

Needless to say, in the case of a polymerization performed in a singlesolvent, this solvent is the solvent that is in major amount.

The block polymer according to the invention comprises at least a firstblock and at least a second block that are connected together via anintermediate segment comprising at least one constituent monomer of thefirst block and at least one constituent monomer of the second block.The intermediate segment (also known as the intermediate block) has aglass transition temperature Tg that is between the glass transitiontemperatures of the first and second blocks.

The intermediate segment is a block comprising at least one constituentmonomer of the first block and at least one constituent monomer of thesecond block of the polymer allowing these blocks to be“compatibilized”.

Advantageously, the intermediate segment comprising at least oneconstituent monomer of the first block and at least one constituentmonomer of the second block of the block polymer is a statisticalpolymer.

Preferably, the intermediate block is derived essentially fromconstituent monomers of the first block and of the second block.

The term “essentially” means at least 85%, preferably at least 90%,better still 95% and even better still 100%.

The block polymer according to the invention is advantageously afilm-forming block ethylenic polymer.

The term “ethylenic” polymer means a polymer obtained by polymerizationof ethylenically unsaturated monomers.

The term “film-forming polymer” means a polymer that is capable offorming, by itself or in the presence of an auxiliary film-formingagent, a continuous deposit on a support, especially on keratinmaterials.

Preferentially, the polymer according to the invention does not compriseany silicon atoms in its backbone. The term “backbone” means the mainchain of the polymer, as opposed to the pendent side chains.

Preferably, the polymer according to the invention is not water-soluble,i.e. the polymer is not soluble in water or in a mixture of water andlinear or branched lower monoalcohols containing from 2 to 5 carbonatoms, for instance ethanol, isopropanol or n-propanol, withoutmodifying the pH, at the solids content of at least 1% by weight, atroom temperature (25° C.).

Preferably, the polymer according to the invention is not an elastomer.

The term “non-elastomeric polymer” means a polymer which, when it issubjected to a constraint intended to stretch it (for example by 30%relative to its initial length), it does not return to a lengthsubstantially identical to its initial length when the constraintceases.

More specifically, the term “non-elastomeric polymer” denotes a polymerwith an instantaneous recovery R_(i)<50% and a delayed recoveryR_(2h)<70% after having been subjected to a 30% elongation. Preferably,R, is <30% and R_(2h)<50%.

More specifically, the non-elastomeric nature of the polymer isdetermined according to the following protocol:

A polymer film is prepared by pouring a solution of the polymer in aTeflon-coated mould, followed by drying for 7 days in an environmentconditioned at 23±5° C. and 50±10% relative humidity.

A film about 100 μm thick is thus obtained, from which are cutrectangular specimens (for example using a punch) 15 mm wide and 80 mmlong.

This sample is subjected to a tensile stress using a machine sold underthe reference Zwick, under the same temperature and humidity conditionsas for the drying.

The specimens are pulled at a speed of 50 mm/min and the distancebetween the jaws is 50 mm, which corresponds to the initial length (I₀)of the specimen.

The instantaneous recovery Ri is determined in the following manner:

-   -   the specimen is pulled by 30% (ε_(max)), i.e. about 0.3 times        its initial length (I₀)    -   the constraint is released by applying a return speed equal to        the tensile speed, i.e. 50 mm/min, and the residual elongation        of the specimen is measured as a percentage, after returning to        zero constraint (ε_(i)).

The percentage instantaneous recovery (R_(i)) is given by the followingformula:

R _(i)(ε_(max)−ε_(i))/ε_(max))×100

To determine the delayed recovery, the percentage residual elongation ofthe specimen (ε_(2h)) is measured 2 hours after returning to zeroconstraint.

The percentage delayed recovery (R_(2h)) is given by the followingformula:

R _(2h)(ε_(max)−ε_(2h))/ε_(max))×100

Purely as a guide, a polymer according to one embodiment of theinvention preferably has an instantaneous recovery R_(i) of 10% and adelayed recovery R_(2h) of 30%.

The polydispersity index of the polymer of the invention is greater than2.

Advantageously, the block polymer used in the compositions according tothe invention has a polydispersity index I of greater than 2, forexample ranging from 2 to 9, preferably greater than or equal to 2.5,for example ranging from 2.5 to 8 and better still greater than or equalto 2.8, and especially ranging from 2.8 to 6.

The polydispersity index I of the polymer is equal to the ratio of theweight-average molecular mass Mw to the number-average molecular massMn.

The weight-average molar mass (Mw) and number-average molar mass (Mn)are determined by gel permeation liquid chromatography (THF solvent,calibration curve established with linear polystyrene standards,refractometric detector).

The weight-average mass (Mw) of the polymer according to the inventionis preferably less than or equal to 300 000; it ranges, for example,from 35 000 to 200 000 and better still from 45 000 to 150 000 g/mol.

The number-average mass (Mn) of the polymer according to the inventionis preferably less than or equal to 70 000; it ranges, for example, from10 000 to 60 000 and better still from 12 000 to 50 000 g/mol.

Preferably, the polydispersity index of the polymer according to theinvention is greater than 2, for example ranging from 2 to 9, preferablygreater than or equal to 2.5, for example ranging from 2.5 to 8 andbetter still greater than or equal to 2.8, and especially ranging from2.8 to 6.

First Block with a Tg of Greater than or Equal to 40° C.,

The block with a Tg of greater than or equal to 40° C. has, for example,a Tg ranging from 40 to 150° C., preferably greater than or equal to 50°C., for example ranging from 50° C. to 120° C. and better still greaterthan or equal to 60° C., for example ranging from 60° C. to 120° C.

The glass transition temperatures indicated for the first and secondblocks may be theoretical Tg values determined from the theoretical Tgvalues of the constituent monomers of each of the blocks, which may befound in a reference manual such as the Polymer Handbook, 3rd Edition,1989, John Wiley, according to the following relationship, known asFox's law:

1/Tg=Σ( ω _(i) /Tg _(i)),i

ω _(i) being the mass fraction of the monomer i in the block underconsideration and Tg_(i) being the glass transition temperature of thehomopolymer of the monomer i.

Unless otherwise indicated, the Tg values indicated for the first andsecond blocks in the present patent application are theoretical Tgvalues.

The difference between the glass transition temperatures of the firstand second blocks is generally greater than 10° C., preferably greaterthan 20° C. and better still greater than 30° C.

In the present invention, the expression: “between . . . and . . . ” isintended to denote a range of values for which the limits mentioned areexcluded, and “from . . . to . . . ” and “ranging from . . . to . . . ”are intended to denote a range of values for which the limits areincluded.

The block with a Tg of greater than or equal to 40° C. may be ahomopolymer or a copolymer.

The block with a Tg of greater than or equal to 40° C. may be derivedtotally or partially from one or more monomers which are such that thehomopolymer prepared from these monomers has a glass transitiontemperature of greater than or equal to 40° C. This block may also bereferred to as a “rigid block”.

In the case where this block is a homopolymer, it is derived frommonomers which are such that the homopolymers prepared from thesemonomers have glass transition temperatures of greater than or equal to40° C. This first block may be a homopolymer consisting of only one typeof monomer (for which the Tg of the corresponding homopolymer is greaterthan or equal to 40° C.).

In the case where the first block is a copolymer, it may be totally orpartially derived from one or more monomers, the nature andconcentration of which are chosen such that the Tg of the resultingcopolymer is greater than or equal to 40° C.

The copolymer may comprise, for example:

-   -   monomers which are such that the homopolymers prepared from        these monomers have Tg values of greater than or equal to 40°        C., for example a Tg ranging from 40 to 150° C., preferably        greater than or equal to 50° C., for example ranging from 50° C.        to 120° C. and better still greater than or equal to 60° C., for        example ranging from 60° C. to 120° C., and    -   monomers which are such that the homopolymers prepared from        these monomers have Tg values of less than 40° C., chosen from        monomers with a Tg of between 20° C. and 40° C. and/or monomers        with a Tg of less than or equal to 20° C., for example a Tg        ranging from −100° C. to 20° C., preferably less than 15° C.,        especially ranging from −80° C. to 15° C. and better still less        than 10° C., for example ranging from −50° C. to 0° C., as        described later.

The first monomers whose homopolymers have a glass transitiontemperature of greater than or equal to 40° C. are chosen, preferably,from the following monomers, also known as the main monomers:

-   -   the methacrylates of formula CH₂═C(CH₃)—COOR₁

in which R₁ represents a linear or branched unsubstituted alkyl groupcontaining from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl orisobutyl group or R₁ represents a C₄ to C₁₂ cycloalkyl group, preferablya C₈ to C₁₂ cycloalkyl, such as isobornyl methacrylate,

-   -   the acrylates of formula CH₂═CH—COOR₂

in which R₂ represents a C₄ to C₁₂ cycloalkyl group such as an isobornylgroup or a tert-butyl group,

-   -   the (meth)acrylamides of formula:

in which R₇ and R₈, which may be identical or different, each representa hydrogen atom or a linear or branched C₁ to C₁₂ alkyl group such as ann-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; or R₇represents H and R₈ represents a 1,1-dimethyl-3-oxobutyl group, and

-   -   R′ denotes H or methyl. Examples of monomers that may be        mentioned include N-butylacrylamide, N-tert-butylacrylamide,        N-isopropylacrylamide, N,N-dimethylacrylamide and        N,N-dibutylacrylamide, and mixtures thereof.

The first block is advantageously obtained from at least one acrylatemonomer of formula CH₂═CH—COOR₂ and from at least one methacrylatemonomer of formula CH₂═C(CH₃)—COOR₂ in which R₂ represents a C₄ to C₁₂cycloalkyl group, preferably a C₈ to C₁₂ cycloalkyl, such as isobornyl.The monomers and the proportions thereof are preferably chosen such thatthe glass transition temperature of the first block is greater than orequal to 40° C.

According to one embodiment, the first block is obtained from:

i) at least one acrylate monomer of formula CH₂═CH—COOR₂ in which R₂represents a C₄ to C₁₂ cycloalkyl group, preferably a C₈ to C₁₂cycloalkyl, such as isobornyl,

ii) and at least one methacrylate monomer of formula CH₂═C(CH₃)—COOR′₂in which R′₂ represents a C₄ to C₁₂ cycloalkyl group, preferably a C₈ toC₁₂ cycloalkyl, such as isobornyl.

According to one embodiment, the first block is obtained from at leastone acrylate monomer of formula CH₂═CH—COOR₂ in which R₂ represents a C₈to C₁₂ cycloalkyl group, such as isobornyl, and from at least onemethacrylate monomer of formula CH₂═C(CH₃)—COOR′₂ in which R₂ representsa C₈ to C₁₂ cycloalkyl group, such as isobornyl.

Preferably, R₂ and R′₂ represents, independently or simultaneously, anisobornyl group.

Preferably, the block copolymer comprises from 50% to 80% by weight ofisobornyl methacrylate/acrylate, from 10% to 30% by weight of isobutylacrylate and from 2% to 10% by weight of acrylic acid.

The first block may be obtained exclusively from the said acrylatemonomer and from the said methacrylate monomer.

The acrylate monomer and the methacrylate monomer are preferably in massproportions of between 30/70 and 70/30, preferably between 40/60 and60/40, especially about 50/50.

The proportion of the first block advantageously ranges from 20% to 90%,better still from 30% to 80% and even better still from 60% to 80% byweight of the polymer.

According to one embodiment, the first block is obtained bypolymerization of isobornyl methacrylate and isobornyl acrylate.

Second block with a glass transition temperature of less than 20° C. Thesecond block advantageously has a glass transition temperature Tg ofless than or equal to 20° C., for example, a Tg ranging from −100° C. to20° C., preferably less than or equal to 15° C., especially ranging from−80° C. to 15° C. and better still less than or equal to 10° C., forexample ranging from −100° C. to 10° C., especially ranging from −30° C.to 10° C.

The second block is totally or partially derived from one or more secondmonomers, which are such that the homopolymer prepared from thesemonomers has a glass transition temperature of less than or equal to 20°C.

This block may also be referred to as a “flexible block”.

The monomer with a Tg of less than or equal to 20° C. (known as thesecond monomer) is preferably chosen from the following monomers:

-   -   the acrylates of formula CH₂═CHCOOR₃, R₃ representing a linear        or branched C₁ to C₁₂ unsubstituted alkyl group, with the        exception of the tert-butyl group, in which one or more        heteroatoms chosen from O, N and S are optionally intercalated,    -   the methacrylates of formula CH₂═C(CH₃)—COOR₄, R₄ representing a        linear or branched C₆ to C₁₂ unsubstituted alkyl group, with the        exception of the tert-butyl group, in which one or more        heteroatoms chosen from O, N and S are optionally intercalated,    -   the vinyl esters of formula R₅—CO—O—CH═CH₂, in which R₅        represents a linear or branched C₄ to C₁₂ alkyl group,    -   ethers of vinyl alcohol and of a C₄ to C₁₂ alcohol,    -   N—(C₄ to C₁₂)alkyl acrylamides, such as N-octylacrylamide,    -   and mixtures thereof.

The preferred monomers with a Tg of less than or equal to 20° C. areisobutyl acrylate, 2-ethylhexyl acrylate or mixtures thereof in allproportions.

Each of the first and second blocks may contain in small proportion atleast one constituent monomer of the other block.

Thus, the first block may contain at least one constituent monomer ofthe second block, and vice versa.

Each of the first and/or second blocks may comprise, in addition to themonomers indicated above, one or more other monomers known as additionalmonomers, which are different from the main monomers mentioned above.

The nature and amount of this or these additional monomer(s) are chosensuch that the block in which they are present has the desired glasstransition temperature.

This additional monomer is chosen, for example, from:

-   -   ethylenically unsaturated monomers comprising at least one        tertiary amine function, such as 2-vinylpyridine,        4-vinylpyridine, dimethylaminoethyl methacrylate,        diethylaminoethyl methacrylate,        dimethylaminopropylmethacrylamide, and salts thereof,    -   the methacrylates of formula CH₂═C(CH₃)—COOR₆ in which R₆        represents a linear or branched alkyl group containing from 1 to        4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl        group, the said alkyl group being substituted with one or more        substituents chosen from hydroxyl groups (for instance        2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate)        and halogen atoms (Cl, Br, I or F), such as trifluoroethyl        methacrylate,    -   the methacrylates of formula CH₂═C(CH₃)—COOR₉, R₉ representing a        linear or branched C₆ to C₁₂ alkyl group in which one or more        heteroatoms chosen from O, N and S are optionally intercalated,        the said alkyl group being substituted with one or more        substituents chosen from hydroxyl groups and halogen atoms (Cl,        Br, I or F),    -   the acrylates of formula CH₂═CHCOOR₁₀, R₁₀ representing a linear        or branched C₁ to C₁₂ alkyl group substituted with one or more        substituents chosen from hydroxyl groups and halogen atoms (Cl,        Br, I and F), such as 2-hydroxypropyl acrylate and        2-hydroxyethyl acrylate, or R₁₀ represents a C₁ to C₁₂        alkyl-O-POE (polyoxyethylene) with repetition of the oxyethylene        unit 5 to 10 times, for example methoxy-POE, or R₈ represents a        polyoxyethylenated group comprising from 5 to 10 ethylene oxide        units.

In particular, the first block may comprise as additional monomer:

-   -   (meth)acrylic acid, preferably acrylic acid,    -   tert-butyl acrylate,    -   the methacrylates of formula CH₂═C(CH₃)—COOR₁, in which R₁        represents a linear or branched unsubstituted alkyl group        containing from 1 to 4 carbon atoms, such as a methyl, ethyl,        propyl or isobutyl group,    -   the (meth)acrylamides of formula:

in which R₇ and R₈, which may be identical or different, each representa hydrogen atom or a linear or branched C₁ to C₁₂ alkyl group such as ann-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; or R₇represents H and R₈ represents a 1,1-dimethyl-3-oxobutyl group, and

-   -   R′ denotes H or methyl. Examples of monomers that may be        mentioned include N-butylacrylamide, N-tert-butylacrylamide,        N-isopropylacrylamide, N,N-dimethylacrylamide and        N,N-dibutylacrylamide,        -   and mixtures thereof

The additional monomer may represent 0.5% to 30% by weight relative tothe weight of the polymer. According to one embodiment, the polymer ofthe invention does not contain any additional monomer.

Preferably, the polymer of the invention comprises at least isobornylacrylate and isobornyl methacrylate monomers in the first block andisobutyl acrylate and acrylic acid monomers in the second block.

Preferably, the polymer comprises at least isobornyl acrylate andisobornyl methacrylate monomers in equivalent weight proportion in thefirst block and isobutyl acrylate and acrylic acid monomers in thesecond block.

Preferably, the polymer comprises at least isobornyl acrylate andisobornyl methacrylate monomers in equivalent weight proportion in thefirst block and isobutyl acrylate and acrylic acid monomers in thesecond block, the first block representing 70% by weight of the polymer.

Preferably, the polymer comprises at least isobornyl acrylate andisobornyl methacrylate monomers in equivalent weight proportion in thefirst block and isobutyl acrylate and acrylic acid monomers in thesecond block. Preferably, the block with a Tg of greater than 40° C.represents 70% by weight of the polymer, and acrylic acid represents 5%by weight of the polymer.

According to one embodiment, the first block does not comprise anyadditional monomer.

According to a preferred embodiment, the second block comprises acrylicacid as additional monomer. In particular, the second block isadvantageously obtained from an acrylic acid monomer and from at leastone other monomer with a Tg of less than or equal to 20° C.

The block copolymer may advantageously comprise more than 2% by weightof acrylic acid monomers, and especially from 2% to 15% by weight, forexample from 3% to 15% by weight, in particular from 4% to 15% by weightor even from 4% to 10% by weight of acrylic acid monomers, relative tothe total weight of the said copolymer.

The constituent monomers of the second block and the proportions thereofare preferably chosen such that the glass transition temperature of thesecond block is less than or equal to 20° C.

Intermediate Segment

The intermediate segment (also known as the intermediate block) connectsthe first block and the second block of the polymer used according tothe present invention. The intermediate segment results from thepolymerization:

i) of the first monomer(s), and optionally of the additional monomer(s),which remain available after their polymerization to a maximum degree ofconversion of 90% to form the first block,

ii) and of the second monomer(s), and optionally of the additionalmonomer(s), added to the reaction mixture.

The formation of the second block is initiated when the first monomersno longer react or are no longer incorporated into the polymer chaineither because they are all consumed or because their reactivity nolonger allows them to be.

Thus, the intermediate segment comprises the first available monomers,resulting from a degree of conversion of these first monomers of lessthan or equal to 90%, during the introduction of the second monomer(s)during the synthesis of the polymer.

The intermediate segment of the block polymer is a statistical polymer(which may also be referred to as a statistical block). This means thatit comprises a statistical distribution of the first monomer(s) and ofthe second monomer(s) and also of the additional monomer(s) that may bepresent.

Thus, the intermediate segment is a statistical block, as are the firstblock and the second block if they are not homopolymers (i.e. if theyare both formed from at least two different monomers).

Process for Preparing the Copolymer

The block ethylenic copolymer according to the invention is prepared byfree radical polymerization, according to the techniques that are wellknown for this type of polymerization.

The free radical polymerization is performed in the presence of aninitiator, whose nature is adapted, in a known manner, as a function ofthe desired polymerization temperature and of the polymerizationsolvent. In particular, the initiator may be chosen from initiatorscontaining a peroxide function, redox couples, or other radicalpolymerization initiators known to those skilled in the art.

In particular, examples of initiators containing a peroxide functionthat may be mentioned include:

-   -   a. peroxyesters, such as tert-butyl peroxyacetate, tert-butyl        perbenzoate, tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S        from Akzo Nobel) and        2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141        from Akzo Nobel);    -   b. peroxydicarbonates, such as diisopropyl peroxydicarbonate;    -   c. peroxy ketones, such as methyl ethyl ketone peroxide;    -   d. hydroperoxides, such as hydrogen peroxide (H₂O₂) and        tert-butyl hydroperoxide;    -   e. diacyl peroxides, such as acetyl peroxide and benzoyl        peroxide;    -   f. dialkyl peroxides, such as di-tert-butyl peroxide;    -   g. inorganic peroxides, such as potassium peroxodisulfate        (K₂S₂O₈).

An example of an initiator in the form of a redox couple that may bementioned is the potassium thiosulfate+potassium peroxodisulfate couple.

According to one preferred embodiment, the initiator is chosen fromorganic peroxides comprising from 8 to 30 carbon atoms. Preferably, theinitiator used is 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane soldunder the reference Trigonox® 141 by the company Akzo Nobel.

The block copolymer used according to the invention is prepared byfree-radical polymerization rather than by controlled or livingpolymerization. In particular, the polymerization of the block ethyleniccopolymer is performed in the absence of control agents, and inparticular in the absence of control agents conventionally used inliving or controlled polymerization processes, for instance nitroxides,alkoxyamines, dithioesters, dithiocarbamates, dithiocarbonates orxanthates, trithiocarbonates and copper-based catalysts.

As indicated previously, the intermediate segment is a statisticalblock, as are the first block and the second block if they are nothomopolymers (i.e. if they are both formed from at least two differentmonomers).

The block copolymer may be prepared by free-radical polymerization, andin particular via a process that consists in mixing, in the samereactor, a polymerization solvent, an initiator, at least one monomerwith a glass transition temperature of greater than or equal to 40° C.and at least one monomer with a glass transition temperature of lessthan or equal to 20° C., according to the following sequence:

-   -   some of the polymerization solvent and optionally some of the        initiator and of the monomers of the first addition are placed        in the reactor, and the mixture is heated to a reaction        temperature of between 60 and 120° C.,    -   the said at least one first monomer with a Tg of greater than or        equal to 40° C. and optionally some of the initiator are then        introduced, in a first addition, and the mixture is left to        react for a time T corresponding to a maximum degree of        conversion of the said monomers of 90%,    -   more polymerization initiator and the said at least one second        monomer with a glass transition temperature of less than or        equal to 20° C. are then placed in the reactor, in a second        addition, and the mixture is left to react for a time T′ after        which the degree of conversion of the said monomers reaches a        plateau,    -   the reaction mixture is cooled to room temperature.

Preferably, the copolymer may be prepared by free-radicalpolymerization, in particular via a process that consists in mixing, inthe same reactor, a polymerization solvent, an initiator, an acrylicacid monomer, at least one monomer with a glass transition temperatureof less than or equal to 20° C., at least one acrylate monomer offormula CH₂═CH—COOR₂ in which R₂ represents a C₄ to C₁₂ cycloalkylgroup, and at least one methacrylate monomer of formulaCH₂═C(CH₃)—COOR′₂ in which R′₂ represents a C₄ to C₁₂ cycloalkyl group,according to the following sequence of steps:

some of the polymerization solvent and optionally some of the initiatorand of the monomers of the first addition are placed in the reactor, andthe mixture is heated to a reaction temperature of between 60 and 120°C.,

the said at least one acrylate monomer of formula CH₂═CH—COOR₂ and thesaid at least one methacrylate monomer of formula CH₂═C(CH₃)—COOR′₂ asmonomers with a Tg of greater than or equal to 40° C., and optionallysome of the initiator, are then introduced, in a first addition, and themixture is left to react for a time T corresponding to a maximum degreeof conversion of the said monomers of 90%,

more polymerization initiator, the acrylic acid monomer and the said atleast one second monomer with a glass transition temperature of lessthan or equal to 20° C. are then placed in the reactor, in a secondaddition, and the mixture is left to react for a time T′ after which thedegree of conversion of the said monomers reaches a plateau,

the reaction mixture is cooled to room temperature.

The term “polymerization solvent” means a solvent or a mixture ofsolvents. In particular, as polymerization solvents that may be used,mention may be made of:

-   -   ketones that are liquid at room temperature, such as methyl        ethyl ketone, methyl isobutyl ketone, diisobutyl ketone,        isophorone, cyclohexanone or acetone;    -   propylene glycol ethers that are liquid at room temperature,        such as propylene glycol monomethyl ether, propylene glycol        monomethyl ether acetate or dipropylene glycol mono-n-butyl        ether;    -   short-chain esters (containing from 3 to 8 carbon atoms in        total) such as ethyl acetate, methyl acetate, propyl acetate,        n-butyl acetate or isopentyl acetate;    -   ethers that are liquid at room temperature, such as diethyl        ether, dimethyl ether or dichlorodiethyl ether;    -   alkanes that are liquid at room temperature, such as decane,        heptane, dodecane, isododecane, cyclohexane or isohexadecane;    -   cyclic aromatic compounds that are liquid at room temperature,        such as toluene or xylene; aldehydes that are liquid at room        temperature, such as benzaldehyde or acetaldehyde; and mixtures        thereof.

Conventionally, the polymerization solvent is a volatile oil with aflash point of less than 80° C. The flash point is measured inparticular according to standard ISO 3679.

The polymerization solvent may be chosen especially from ethyl acetate,butyl acetate, alcohols such as isopropanol or ethanol, and aliphaticalkanes such as isododecane, and mixtures thereof. Preferably, thepolymerization solvent is a mixture of butyl acetate and isopropanol orisododecane.

According to another embodiment, the copolymer may be prepared byfree-radical polymerization according to a preparation process thatconsists in mixing, in the same reactor, a polymerization solvent, aninitiator, at least one monomer with a glass transition temperature ofless than or equal to 20° C., and at least one monomer with a Tg ofgreater than or equal to 40° C., according to the following sequence ofsteps:

-   -   some of the polymerization solvent and optionally some of the        initiator and of the monomers of the first addition are placed        in the reactor, and the mixture is heated to a reaction        temperature of between 60 and 120° C.,    -   the said at least one monomer with a glass transition        temperature of less than or equal to 20° C. and optionally some        of the initiator are then introduced, in a first addition, and        the mixture is left to react for a time T corresponding to a        maximum degree of conversion of the said monomers of 90%,    -   more polymerization initiator and the said at least one monomer        with a Tg of greater than or equal to 40° C. are then placed in        the reactor, in a second addition, and the mixture is left to        react for a time T′ after which the degree of conversion of the        said monomers reaches a plateau,    -   the reaction mixture is cooled to room temperature.

According to one preferred embodiment, the copolymer may be prepared byfree-radical polymerization according to a preparation process thatconsists in mixing, in the same reactor, a polymerization solvent, aninitiator, an acrylic acid monomer, at least one monomer with a glasstransition temperature of less than or equal to 20° C., at least onemonomer with a Tg of greater than or equal to 40° C., and, in particularas monomers with a Tg of greater than or equal to 40° C., at least oneacrylate monomer of formula CH₂═CH—COOR₂ in which R₂ represents a C₄ toC₁₂ cycloalkyl group, and at least one methacrylate monomer of formulaCH₂═C(CH₃)—COOR′₂ in which R′₂ represents a C₄ to C₁₂ cycloalkyl group,according to the following sequence of steps:

-   -   some of the polymerization solvent and optionally some of the        initiator and of the monomers of the first addition are placed        in the reactor, and the mixture is heated to a reaction        temperature of between 60 and 120° C.,    -   the acrylic acid monomer and the said at least one monomer with        a glass transition temperature of less than or equal to 20° C.        and optionally some of the initiator are then introduced, in a        first addition, and the mixture is left to react for a time T        corresponding to a maximum degree of conversion of the said        monomers of 90%,    -   more polymerization initiator, the said at least one acrylate        monomer of formula CH₂═CH—COOR₂ and the said at least one        methacrylate monomer of formula CH₂═C(CH₃)—COOR′₂ as monomers        with a Tg of greater than or equal to 40° C. are then placed in        the reactor, in a second addition, and the mixture is left to        react for a time T′ after which the degree of conversion of the        said monomers reaches a plateau,    -   the reaction mixture is cooled to room temperature.

The polymerization temperature is preferably about 90° C.

The reaction time after the second addition is preferably between 3 and6 hours.

Preferably, the block ethylenic copolymer is present in the compositionin an active material content ranging from 0.1% to 60%, better stillfrom 0.5% to 50%, better still from 1% to 30% and even better still from1% to 40% by weight relative to the total weight of the composition.

Distillation of the Synthesis Solvent

It is possible to perform a step of total or partial removal of the saidvolatile oil or solvent (conventionally isododecane). This is thenperformed in particular by distillation, optionally under vacuum, andoptional addition of non-volatile hydrocarbon-based ester oil comprisingat least 16 carbon atoms and having a molar mass of less than 650 g/mol,such as octyldodecyl neopentanoate (especially 2-octyldodecylneopentanoate).

This step is performed at elevated temperature and optionally undervacuum to distil off a maximum amount of volatile synthesis solvent, andis known to those skilled in the art.

Polyamide Silicone Block Polymer

According to another embodiment variant, a composition according to theinvention comprises, as hydrophobic film-forming polymer, at least onepolyamide silicone block polymer, also known as a silicone polyamide.

The silicone polyamides are preferably solid at room temperature (25°C.) and atmospheric pressure (760 mmHg).

For the purposes of the invention, the term “polymer” means a compoundcontaining at least two repeating units, preferably at least threerepeating units and better still ten repeating units.

The silicone polyamides of the composition of the invention may bepolymers of the polyorganosiloxane type, for instance those described indocuments U.S. Pat. No. 5,874,069, U.S. Pat. No. 5,919,441, U.S. Pat.No. 6,051,216 and U.S. Pat. No. 5,981,680. According to the invention,the silicone polymers may belong to the following two families:

(1) polyorganosiloxanes comprising at least two amide groups, these twogroups being located in the polymer chain, and/or

(2) polyorganosiloxanes comprising at least two amide groups, these twogroups being located on grafts or branches.

According to a first variant, the silicone polymers arepolyorganosiloxanes as defined above in which the units capable ofestablishing hydrogen interactions are located in the polymer chain.

The silicone polymers may more particularly be polymers comprising atleast one unit corresponding to the general formula I:

in which:

R4, R5, R6 and R7, which may be identical or different, represent agroup chosen from:

linear, branched or cyclic, saturated or unsaturated, C₁ to C₄₀hydrocarbon-based groups, possibly containing in their chain one or moreoxygen, sulfur and/or nitrogen atoms, and possibly being partially ortotally substituted with fluorine atoms,

C₆-C₁₀ aryl groups, optionally substituted with one or more C₁-C₄ alkylgroups,

polyorganosiloxane chains possibly containing one or more oxygen, sulfurand/or nitrogen atoms,

the groups X, which may be identical or different, represent a linear orbranched C1 to C30 alkylenediyl group, possibly containing in its chainone or more oxygen and/or nitrogen atoms;

Y is a saturated or unsaturated C1 to C50 linear or branched alkylene,arylene, cycloalkylene, alkylarylene or arylalkylene divalent group,which may comprise one or more oxygen, sulfur and/or nitrogen atomsand/or which may bear as substituent one of the following atoms orgroups of atoms: fluorine, hydroxyl, C3 to C8 cycloalkyl, C1 to C40alkyl, C5 to C10 aryl, phenyl optionally substituted with 1 to 3 C1 toC3 alkyl, C1 to C3 hydroxyalkyl and C1 to C6 aminoalkyl groups, or

Y represents a group corresponding to the formula:

in which:

T represents a linear or branched, saturated or unsaturated, C3 to C24trivalent or tetravalent hydrocarbon-based group optionally substitutedwith a polyorganosiloxane chain, and possibly containing one or moreatoms chosen from O, N and S, or T represents a trivalent atom chosenfrom N, P and Al, and

R8 represents a linear or branched C1 to C50 alkyl group or apolyorganosiloxane chain, possibly comprising one or more ester, amide,urethane, thiocarbamate, urea, thiourea and/or sulfonamide groups, whichmay possibly be linked to another chain of the polymer;

the groups G, which may be identical or different, represent divalentgroups chosen from:

in which R9 represents a hydrogen atom or a linear or branched C1 to C20alkyl group, on condition that at least 50% of the groups R9 of thepolymer represent a hydrogen atom and that at least two of the groups Gof the polymer are a group other than:

n is an integer ranging from 2 to 500 and preferably from 2 to 200, andm is an integer ranging from 1 to 1000, preferably from 1 to 700 andbetter still from 6 to 200.

According to the invention, 80% of the groups R4, R5, R6 and R7 of thepolymer are preferably chosen from methyl, ethyl, phenyl and3,3,3-trifluoropropyl groups.

According to the invention, Y can represent various divalent groups,furthermore optionally comprising one or two free valencies to establishbonds with other units of the polymer or copolymer. Preferably, Yrepresents a group chosen from:

C1 to C20 and preferably C1 to C10 linear alkylene groups,

C30 to C56 branched alkylene groups possibly comprising rings andunconjugated unsaturations,

C5 to C6 cycloalkylene groups,

phenylene groups optionally substituted with one or more C1 to C40 alkylgroups,

C1 to C20 alkylene groups comprising from 1 to 5 amide groups,

C1 to C20 alkylene groups comprising one or more substituents chosenfrom hydroxyl, C3 to C8 cycloalkane, C1 to C3 hydroxyalkyl and C1 to C6alkylamine groups,

polyorganosiloxane chains of formula:

in which R4, R5, R6, R7, T and m are as defined above, and

polyorganosiloxane chains of formula:

According to the second variant, the polyorganosiloxanes may be polymerscomprising at least one unit corresponding to formula (II):

in which:

R4 and R6, which may be identical or different, are as defined above forformula (I),

R10 represents a group as defined above for R4 and R6, or represents agroup of formula —X-G-R12 in which X and G are as defined above forformula (I) and R12 represents a hydrogen atom or a linear, branched orcyclic, saturated or unsaturated, C1 to C50 hydrocarbon-based groupoptionally comprising in its chain one or more atoms chosen from O, Sand N, optionally substituted with one or more fluorine atoms and/or oneor more hydroxyl groups, or a phenyl group optionally substituted withone or more C1 to C4 alkyl groups,

R11 represents the group of formula —X-G-R12 in which X, G and R12 areas defined above,

m1 is an integer ranging from 1 to 998, and

m2 is an integer ranging from 2 to 500.

According to the invention, the silicone polymer used as structuringagent may be a homopolymer, i.e. a polymer comprising several identicalunits, in particular units of formula (I) or of formula (II).

According to the invention, it is also possible to use a siliconepolymer formed from a copolymer comprising several different units offormula (I), i.e. a polymer in which at least one of the groups R4, R5,R6, R7, X, G, Y, m and n is different in one of the units. The copolymermay also be formed from several units of formula (II), in which at leastone of the groups R4, R6, R10, R11, m1 and m2 is different in at leastone of the units.

It is also possible to use a polymer comprising at least one unit offormula (I) and at least one unit of formula (II), the units of formula(I) and the units of formula (II) possibly being identical to ordifferent from each other.

According to one variant, it is also possible to use a polymerfurthermore comprising at least one hydrocarbon-based unit comprisingtwo groups capable of establishing hydrogen interactions, chosen fromester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane,thiourea, oxamido, guanidino and biguanidino groups, and combinationsthereof

These copolymers may be block polymers or grafted polymers.

According to one advantageous embodiment of the invention, the groupscapable of establishing hydrogen interactions are amide groups offormulae —C(O)NH— and —HN—C(O)—. In this case, the structuring agent maybe a polymer comprising at least one unit of formula (III) or (IV):

in which R4, R5, R6, R7, X, Y, m and n are as defined above.

Such a unit may be obtained:

either by a condensation reaction between a silicone containing a,co-carboxylic acid end units and one or more diamines, according to thefollowing reaction scheme:

or by reaction of two unsaturated α carboxylic acid molecules with adiamine according to the following reaction scheme:

CH₂═CH—X¹—COOH+H₂N—Y—NH₂→CH₂═CH—X¹—CO—NH—Y—NH—CO—X¹—CH═CH₂

followed by the addition of a siloxane to the ethylenic unsaturations,according to the following scheme:

in which X1-(CH₂)₂— corresponds to X defined above and Y, R4, R5, R6, R7and m are as defined above,

or by reaction of a silicone containing α, ω-NH2 end groups and of adiacid of formula HOOC—Y—COOH according to the following reactionscheme:

In these polyamides of formula (III) or (IV), m ranges from 1 to 700, inparticular from 15 to 500 and especially from 50 to 200, and n ranges inparticular from 1 to 500, preferably from 1 to 100 and better still from4 to 25,

X is preferably a linear or branched alkylene chain containing from 1 to30 carbon atoms, in particular 1 to 20 carbon atoms, especially from 5to 15 carbon atoms and more particularly 10 carbon atoms, and

Y is preferably an alkylene chain that is linear or branched, or whichmay comprise rings and/or unsaturations, containing from 1 to 40 carbonatoms, in particular 1 to 20 carbon atoms and better still from 2 to 6carbon atoms, in particular 6 carbon atoms.

In formulae (III) and (IV), the alkylene group representing X or Y canoptionally contain in its alkylene part at least one of the followingcomponents:

one to five amide, urea, urethane or carbamate groups,

a C5 or C6 cycloalkyl group, and

a phenylene group optionally substituted with 1 to 3 identical ordifferent C1 to C3 alkyl groups.

In formulae (III) and (IV), the alkylene groups may also be substitutedwith at least one component chosen from the group consisting of:

a hydroxyl group,

a C3 to C8 cycloalkyl group,

one to three C1 to C40 alkyl groups,

a phenyl group optionally substituted with one to three C1 to C3 alkylgroups,

a C1 to C3 hydroxyalkyl group, and

a C1 to C6 aminoalkyl group.

In these formulae (III) and (IV), Y may also represent:

in which R8 represents a polyorganosiloxane chain and T represents agroup of formula:

in which a, b and c are, independently, integers ranging from 1 to 10,and R13 is a hydrogen atom or a group such as those defined for R4, R5,R6 and R7.

In formulae (III) and (IV), R4, R5, R6 and R7 preferably represent,independently, a linear or branched C₁ to C₄₀ alkyl group, preferably aCH₃, C₂H₅, n-C₃H₇ or isopropyl group, a polyorganosiloxane chain or aphenyl group optionally substituted with one to three methyl or ethylgroups.

As has been seen previously, the polymer may comprise identical ordifferent units of formula (III) or (IV).

Thus, the polymer may be a polyamide containing several units of formula(III) or (IV) of different lengths, i.e. a polyamide corresponding toformula (V):

in which X, Y, n and R4 to R7 have the meanings given above, m1 and m2,which are different, are chosen in the range from 1 to 1000, and p is aninteger ranging from 2 to 300.

In this formula, the units may be structured to form either a blockcopolymer, or a random copolymer or an alternating copolymer. In thiscopolymer, the units may be not only of different lengths, but also ofdifferent chemical structures, for example containing different groupsY. In this case, the polymer may correspond to formula VI:

in which R4 to R7, X, Y, m1, m2, n and p have the meanings given aboveand Y1 is different from Y but chosen from the groups defined for Y. Aspreviously, the various units may be structured to form either a blockcopolymer, or a random copolymer or an alternating copolymer.

In this first embodiment of the invention, the structuring agent mayalso be formed from a grafted copolymer. Thus, the polyamide containingsilicone units may be grafted and optionally crosslinked with siliconechains containing amide groups. Such polymers may be synthesized withtrifunctional amines.

In this case, the polymer may comprise at least one unit of formula(VII):

in which X1 and X2, which are identical or different, have the meaninggiven for X in formula (I), n is as defined in formula (I), Y and T areas defined in formula (I), R14 to R21 are groups chosen from the samegroup as R4 to R7, m1 and m2 are numbers located in the range from 1 to1000, and p is an integer ranging from 2 to 500.

In formula (VII), the following are preferred:

p ranges from 1 to 25 and better still from 1 to 7,

R14 to R21 are methyl groups,

T corresponds to one of the following formulae:

in which R22 is a hydrogen atom or a group chosen from the groupsdefined for R4 to R7, and R23, R24 and R25 are, independently, linear orbranched alkylene groups, more preferably corresponding to the formula:

in particular with R23, R24 and R25 representing —CH2-CH2-,

m1 and m2 range from 15 to 500 and better still from 15 to 45,

X1 and X2 represent —(CH2)10-, and

Y represents —CH2-.

These polyamides containing a grafted silicone unit of formula (VII) maybe copolymerized with polyamide silicones of formula (II) to form blockcopolymers, alternating copolymers or random copolymers. The weightpercentage of grafted silicone units (VII) in the copolymer may rangefrom 0.5% to 30% by weight.

According to the invention, as has been seen previously, the siloxaneunits may be in the main chain or backbone of the polymer, but they mayalso be present in grafted or pendent chains. In the main chain, thesiloxane units may be in the form of segments as described above. In thependent or grafted chains, the siloxane units may appear individually orin segments.

According to one embodiment variant of the invention, a copolymer ofsilicone polyamide and of hydrocarbon-based polyamide, or a copolymercomprising units of formula (III) or (IV) and hydrocarbon-basedpolyamide units, may be used. In this case, the silicone polyamide unitsmay be located at the ends of the hydrocarbon-based polyamide.

According to one preferred embodiment, the silicone polyamide comprisesunits of formula III, preferably in which the groups R4, R5, R6 and R7represent methyl groups, one from among X and Y represents an alkylenegroup of 6 carbon atoms and the other represents an alkylene group of 11carbon atoms, n representing the degree of polymerization, DP, of thepolymer. By way of example of such silicone polyamides, mention may bemade of the compounds sold by the company Dow Corning under the names DC2-8179 (DP 100) and DC 2-8178 (DP 15), the INCI name of which isNylon-611/dimethicone copolymer.

Advantageously, the composition according to the invention comprises atleast one polydimethylsiloxane block polymer of general formula (I) withan index in of about 15.

More preferably, the composition according to the invention comprises atleast one polymer comprising at least one unit of formula (III) in whichm ranges from 5 to 100, in particular from 10 to 75 and even moreparticularly is about 15; even more preferably, R4, R5, R6 and R7independently represent a linear or branched C₁ to C₄₀ alkyl group,preferably a group CH₃, C₂H₅, n-C₃H₇ or isopropyl in formula (III).

According to one preferred mode, the silicone polyamide sold by thecompany Dow Corning under the name DC 2-8179 (DP 100) is used.

As examples of silicone polymers that may be used, mention may be madeof one of the silicone polyamides obtained in accordance with Examples 1to 3 of document U.S. Pat. No. 5,981,680.

Vinyl Polymer Comprising at Least One Carbosiloxane Dendrimer-Based Unit

According to one particular embodiment, a composition used according tothe invention may comprise, as hydrophobic film-forming polymer, atleast one vinyl polymer comprising at least one carbosiloxanedendrimer-based unit.

The vinyl polymer used according to the invention especially has abackbone and at least one side chain, which comprises a carbosiloxanedendrimer-based unit having a carbosiloxane dendrimer structure.

Vinyl polymers comprising at least one carbosiloxane dendrimer unit asdescribed in patent applications WO 03/045 337 and EP 963 751 by thecompany Dow Corning may be used in particular.

The term “carbosiloxane dendrimer structure” in the context of thepresent invention represents a structure with branched groups of highmolecular masses, the said structure having high regularity in theradial direction starting from the bond to the backbone. Suchcarbosiloxane dendrimer structures are described in the form of a highlybranched siloxane-silylalkylene copolymer in the laid-open Japanesepatent application Kokai 9-171 154.

A vinyl polymer according to the invention may contain carbosiloxanedendrimer-based units that may be represented by the following generalformula:

in which R¹ represents an aryl group or an alkyl group containing from 1to 10 carbon atoms, and X^(i) represents a silylalkyl group which, wheni=1, is represented by the formula:

in which R′ is the same as defined above, R² represents an alkylenegroup containing from 2 to 10 carbon atoms, R³ represents an alkyl groupcontaining from 1 to 10 carbon atoms, X^(i+1) represents a hydrogenatom, an alkyl group containing from 1 to 10 carbon atoms, an aryl groupor the silylalkyl group defined above with i=i+1; i is an integer from 1to 10 which represents the generation of the said silylalkyl group, anda^(i) is an integer from 0 to 3; Y represents a radical-polymerizableorganic group chosen from:

-   -   organic groups containing a methacrylic group or an acrylic        group and that are represented by the formulae:

in which R⁴ represents a hydrogen atom or an alkyl group, R⁵ representsan alkylene group containing from 1 to 10 carbon atoms, such as amethylene group, an ethylene group, a propylene group or a butylenegroup, the methylene group and the propylene group being preferred; and

-   -   organic groups containing a styryl group and that are        represented by the formula:

in which R⁶ represents a hydrogen atom or an alkyl group, R⁷ representsan alkyl group containing from 1 to 10 carbon atoms, such as a methylgroup, an ethyl group, a propyl group or a butyl group, the methyl groupbeing preferred, R⁸ represents an alkylene group containing from 1 to 10carbon atoms, such as a methylene group, an ethylene group, a propylenegroup or a butylene group, the ethylene group being preferred, b is aninteger from 0 to 4, and c is 0 or 1 such that if c is 0, —(R⁸)_(c)—represents a bond.

According to one embodiment, R¹ may represent an aryl group or an alkylgroup containing from 1 to 10 carbon atoms. The alkyl group maypreferably be represented by a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, an isopropyl group, an isobutylgroup, a cyclopentyl group or a cyclohexyl group. The aryl group maypreferably be represented by a phenyl group and a naphthyl group. Themethyl and phenyl groups are more particularly preferred, and the methylgroup is preferred among all.

A vinyl polymer containing at least one carbosiloxane dendrimer-basedunit has a molecular side chain containing a carbosiloxane dendrimerstructure, and may be the product of polymerization of:

(A) from 0 to 99.9 parts by weight of a vinyl monomer; and

(B) from 100 to 0.1 part by weight of a carbosiloxane dendrimercontaining a radical-polymerizable organic group, represented by thegeneral formula:

in which Y represents a radical-polymerizable organic group, R¹represents an aryl group or an alkyl group containing from 1 to 10carbon atoms, and X^(i) represents a silylalkyl group which, when i=1,is represented by the formula:

in which R¹ is the same as defined above, R² represents an alkylenegroup containing from 2 to 10 carbon atoms, R³ represents an alkyl groupcontaining from 1 to 10 carbon atoms, X^(i+1) represents a hydrogenatom, an alkyl group containing from 1 to 10 carbon atoms, an arylgroup, or the silylalkyl group defined above with i=i+1; i is an integerfrom 1 to 10 that represents the generation of the said silylalkylgroup, and a^(i) is an integer from 0 to 3; in which the saidradical-polymerizable organic group contained in the component (B) ischosen from:

-   -   organic groups containing a methacrylic group or an acrylic        group and that are represented by the formulae:

in which R⁴ represents a hydrogen atom or an alkyl group, R⁵ representsan alkylene group containing from 1 to 10 carbon atoms; and organicgroups containing a styryl group and that are represented by theformula:

in which R⁶ represents a hydrogen atom or an alkyl group, R⁷ representsan alkyl group containing from 1 to 10 carbon atoms, R⁸ represents analkylene group containing from 1 to 10 carbon atoms, b is an integerfrom 0 to 4, and c is 0 or 1, such that if c is 0, —(R⁸)_(c)-representsa bond.

The monomer of vinyl type that is the component (A) in the vinyl polymeris a monomer of vinyl type that contains a radical-polymerizable vinylgroup.

There is no particular limitation as regards such a monomer.

The following are examples of this monomer of vinyl type: methylmethacrylate, ethyl methacrylate, n-propyl methacrylate, isopropylmethacrylate or a methacrylate of a lower alkyl analogue; glycidylmethacrylate; butyl methacrylate, butyl acrylate, n-butyl methacrylate,isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate,n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate,2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate,stearyl acrylate, stearyl methacrylate or a higher-analoguemethacrylate; or a higher-analogue methacrylate; vinyl acetate, vinylpropionate or a vinyl ester of a lower fatty acid analogue; vinylcaproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate or anester of a higher fatty acid analogue; styrene, vinyltoluene, benzylmethacrylate, phenoxyethyl methacrylate, vinyl-pyrrolidone or similarvinylaromatic monomers; methacrylamide, N-methylolmethacrylamide,N-methoxymethylmethacrylamide, isobutoxymethoxy-methacrylamide,N,N-dimethylmethacrylamide or similar monomers of vinyl type containingamide groups; hydroxyethyl methacrylate, hydroxypropyl methacrylate orsimilar monomers of vinyl type containing hydroxyl groups; acrylic acidmethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleicacid or similar monomers of vinyl type containing a carboxylic acidgroup; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate,ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate,polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetylvinyl ether, 2-ethylhexyl vinyl ether or a similar monomer of vinyl typewith ether bonds; methacryloxypropyltrimethoxysilane,polydimethylsiloxane containing a methacrylic group on one of itsmolecular ends, polydimethylsiloxane containing a styryl group on one ofits molecular ends, or a similar silicone compound containingunsaturated groups; butadiene; vinyl chloride; vinylidene chloride;methacrylonitrile; dibutyl fumarate; anhydrous maleic acid; anhydroussuccinic acid; methacryl glycidyl ether; an organic salt of an amine, anammonium salt, and an alkali metal salt of methacrylic acid, of itaconicacid, of crotonic acid, of maleic acid or of fumaric acid; aradical-polymerizable unsaturated monomer containing a sulfonic acidgroup such as a styrenesulfonic acid group; a quaternary ammonium saltderived from methacrylic acid, such as2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and amethacrylic acid ester of an alcohol containing a tertiary amine group,such as a methacrylic acid ester of diethylamine.

Multifunctional monomers of vinyl type may also be used.

The following are examples of such compounds: trimethylolpropanetrimethacrylate, pentaerythrityl trimethacrylate, ethylene glycoldimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycoldimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanedioldimethacrylate, neopentyl glycol dimethacrylate,trimethylolpropanetrioxyethyl methacrylate, tris(2-hydroxyethyl)isocyanurate dimethacrylate, tris(2-hydroxyethyl) isocyanuratetrimethacrylate, polydimethylsiloxane capped with styryl groupscontaining divinylbenzene groups on both ends, or similar siliconecompounds containing unsaturated groups.

A carbosiloxane dendrimer, which is the component (B), may berepresented by the following formula:

in which Y represents a radical-polymerizable organic group as definedpreviously.

The following are preferred examples of radical-polymerizable organicgroups Y: an acryloxymethyl group, a 3-acryloxypropyl group, amethacryloxymethyl group, a 3-methacryloxypropyl group, a 4-vinylphenylgroup, a 3-vinylphenyl group, a 4-(2propenyl)phenyl group, a3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a2-(3-vinylphenyl)ethyl group, a vinyl group, an allyl group, a methallylgroup and a 5-hexenyl group.

R′ is as defined previously.

X^(i) represents a silylalkyl group that is represented by the followingformula, when i is equal to 1:

in which R¹ is as defined above.

R² represents an alkylene group containing from 2 to 10 carbon atoms,such as an ethylene group, a propylene group, a butylene group, ahexylene group or a similar linear alkylene group; a methylmethylenegroup, a methylethylene group, a 1-methylpentylene group, a1,4-dimethylbutylene group or a similar branched alkylene group.

The ethylene, methylethylene, hexylene, 1-methylpentylene and1,4-dimethylbutylene groups are preferred above all.

R³ represents an alkyl group containing from 1 to 10 carbon atoms, suchas methyl, ethyl, propyl, butyl and isopropyl groups.

X^(i+1) represents a hydrogen atom, an alkyl group containing from 1 to10 carbon atoms, an aryl group or the silylalkyl group with i=i+1.

a^(i) is an integer from 0 to 3, and i is an integer from 1 to 10 thatindicates the generation number, which represents the number ofrepetitions of the silylalkyl group.

For example, when the generation number is equal to 1, the carbosiloxanedendrimer may be represented by the first general formula shown below,in which Y, R¹, R² and R³ are the same as defined above, R¹² representsa hydrogen atom or is identical to R¹; a¹ is identical to a^(i).Preferably, the mean total number of groups OR³ in a molecule is withinthe range from 0 to 7.

When the generation number is equal to 2, the carbosiloxane dendrimermay be represented by the second general formula shown below, in whichY, R¹, R², R³ and R¹² are the same as defined above; a¹ and a² representthe a′ of the indicated generation. Preferably, the mean total number ofgroups OR³ in a molecule is within the range from 0 to 25.

When the generation number is equal to 3, the carbosiloxane dendrimer isrepresented by the third general formula shown below, in which Y, R¹,R², R³ and R¹² are the same as defined above; a¹, a² and a³ representthe a′ of the indicated generation. Preferably, the mean total number ofgroups OR³ in a molecule is within the range from 0 to 79.

A carbosiloxane dendrimer that contains a radical-polymerizable organicgroup may be represented by the following mean structural formulae:

The carbosiloxane dendrimer may be manufactured according to the processfor manufacturing a branched silalkylene siloxane described in Japanesepatent application Hei 9-171 154.

For example, it may be produced by subjecting an organosilicon compoundcontaining a hydrogen atom linked to a silicon atom, represented by thefollowing general formula:

and an organosilicon compound containing an alkenyl group, to ahydrosilylation reaction.

In the above formula, the organosilicon compound may be represented by3-methacryloxypropyltris(dimethylsiloxy)silane,3-acryloxypropyltris(dimethylsiloxy)silane and4-vinylphenyltris(dimethylsiloxy)silane. The organosilicon compound thatcontains an alkenyl group may be represented byvinyltris(trimethylsiloxy)silane, vinyltris(dimethylphenylsiloxy)silane,and 5-hexenyltris(trimethylsiloxy)silane.

The hydrosilylation reaction is performed in the presence of achloroplatinic acid, a complex of vinylsiloxane and of platinum, or asimilar transition metal catalyst.

A vinyl polymer containing at least one carbosiloxane dendrimer-basedunit may be chosen from polymers such that the carbosiloxanedendrimer-based unit is a carbosiloxane dendritic structure representedby formula (I):

in which Z represents a divalent organic group, “p” is 0 or 1, R¹ is anaryl or alkyl group containing from 1 to 10 carbon atoms and X^(i) is asilylalkyl group represented by formula (II):

in which R¹ is as defined above, R² is an alkylene group containing from1 to 10 carbon atoms, R³ is an alkyl group containing from 1 to 10carbon atoms and X^(i+1) is a group chosen from the group comprisinghydrogen atoms, aryl groups and alkyl groups containing up to 10 carbonatoms, and silylalkyl groups X^(i) in which the power “i” is an integerfrom 1 to 10 indicating the generation of the starting silylalkyl groupin each carbosiloxane dendritic structure with a value of 1 for thegroup X^(i) in formula (I) and the index “a^(i)” is an integer from 0 to3.

In a vinyl polymer containing at least one carbosiloxane dendrimer-basedunit, the polymerization ratio between the components (A) and (B), interms of the weight ratio between (A) and (B), may be within a rangefrom 0/100 to 99.9/0.1, or even from 0.1/99.9 to 99.9/0.1 and preferablywithin a range from 1/99 to 99/1. A ratio between the components (A) and(B) of 0/100 means that the compound becomes a homopolymer of component(B).

A vinyl polymer containing at least one carbosiloxane dendrimer-basedunit may be obtained by copolymerization of the components (A) and (B),or by polymerization of component (B) alone.

The polymerization may be a free-radical polymerization or an ionicpolymerization, but free-radical polymerization is preferred.

The polymerization may be performed by bringing about a reaction betweenthe components (A) and (B) in a solution for a period of from 3 to 20hours in the presence of a radical initiator at a temperature of from50° C. to 150° C.

A suitable solvent for this purpose is hexane, octane, decane,cyclohexane or a similar aliphatic hydrocarbon; benzene, toluene, xyleneor a similar aromatic hydrocarbon; diethyl ether, dibutyl ether,tetrahydrofuran, dioxane or similar ethers; acetone, methyl ethylketone, methyl isobutyl ketone, diisobutyl ketone or similar ketones;methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate orsimilar esters; methanol, ethanol, isopropanol, butanol or similaralcohols; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,hexamethyldisiloxane, octamethyltrisiloxane or a similar organosiloxaneoligomer.

A radical initiator may be any compound known in the art for standardfree-radical polymerization reactions. Specific examples of such radicalinitiators are 2,2′-azobis(isobutyronitrile),2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile) or similar compounds of azobistype; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate,tert-butyl peroxy-2-ethylhexanoate or a similar organic peroxide. Theseradical initiators may be used alone or in a combination of two or more.The radical initiators may be used in an amount of from 0.1 to 5 partsby weight per 100 parts by weight of the components (A) and (B). Achain-transfer agent may be added. The chain-transfer agent may be2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan,3-mercaptopropyltrimethoxysilane, a polydimethylsiloxane containing amercaptopropyl group or a similar compound of mercapto type; methylenechloride, chloroform, carbon tetrachloride, butyl bromide,3-chloropropyltrimethoxysilane or a similar halogenated compound.

In the manufacture of the polymer of vinyl type, after thepolymerization, the residual unreacted vinyl monomer may be removedunder conditions of heating under vacuum.

To facilitate the preparation of the mixture of the starting material ofcosmetic products, the number-average molecular mass of the vinylpolymer containing a carbosiloxane dendrimer may be chosen within therange between 3000 and 2 000 000 and preferably between 5000 and 800000. It may be a liquid, a gum, a paste, a solid, a powder or any otherform. The preferred forms are solutions formed from the dilution of adispersion or of a powder in solvents.

The vinyl polymer may be a dispersion of a polymer of vinyl type havinga carbosiloxane dendrimer structure in its molecular side chain, in aliquid such as a silicone oil, an organic oil, an alcohol or water.

The silicone oil may be a dimethylpolysiloxane with the two molecularends capped with trimethylsiloxy groups, a copolymer ofmethylphenylsiloxane and of dimethylsiloxane having the two molecularends capped with trimethylsiloxy groups, a copolymer ofmethyl-3,3,3-trifluoropropylsiloxane and of dimethylsiloxane having thetwo molecular ends capped with trimethylsiloxy groups, or similarunreactive linear silicone oils, and also hexamethylcyclotrisiloxane,octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane or a similar cyclic compound. In additionto the unreactive silicone oils, modified polysiloxanes containingfunctional groups such as silanol groups, amino groups and polyethergroups on the ends or within the molecular side chains may be used.

The organic oils may be isododecane, liquid paraffin, isoparaffin, hexyllaurate, isopropyl myristate, myristyl myristate, cetyl myristate,2-octyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl palmitate,butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate,cetyl lactate, lanolin acetate, stearyl alcohol, cetostearyl alcohol,oleyl alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojobaoil, gum oil, sunflower oil, soybean oil, camellia oil, squalane, castoroil, cottonseed oil, coconut oil, egg yolk oil, polypropylene glycolmonooleate, neopentyl glycol 2-ethylhexanoate or a similar glycol esteroil; triglyceryl isostearate, the triglyceride of a fatty acid ofcoconut oil, or a similar oil of a polyhydric alcohol ester;polyoxyethylene lauryl ether, polyoxypropylene cetyl ether or a similarpolyoxyalkylene ether.

The alcohol may be any type that is suitable for use in combination witha cosmetic product starting material. For example, it may be methanol,ethanol, butanol, isopropanol or similar lower alcohols.

A solution or a dispersion of the alcohol should have a viscosity withinthe range from 10 to 10⁹ mPa at 25° C. To improve the sensory useproperties in a cosmetic product, the viscosity should be within therange from 100 to 5×10⁸ mPa·s.

The solutions and dispersions may be readily prepared by mixing thevinyl polymer having a carbosiloxane dendrimer structure with a siliconeoil, an organic oil, an alcohol or water. The liquids may be present inthe step of polymerization of a vinyl polymer containing at least onecarbosiloxane dendrimer-based unit. In this case, the unreacted residualvinyl monomer should be completely removed by heat treatment of thesolution or dispersion under atmospheric pressure or reduced pressure.

In the case of a dispersion, the dispersity of the polymer of vinyl typemay be improved by adding a surfactant.

Such an agent may be hexylbenzenesulfonic acid, octylbenzenesulfonicacid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid,cetylbenzenesulfonic acid, myristylbenzenesulfonic acid or anionicsurfactants of the sodium salts of these acids; octyltrimethylammoniumhydroxide, dodecyltrimethylammonium hydroxide,hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammoniumhydroxide, decyldimethylbenzylammonium hydroxide,dioctadecyldimethylammonium hydroxide, beef tallow-trimethylammoniumhydroxide, coconut oil-trimethylammonium hydroxide, or a similarcationic surfactant; a polyoxyalkylene alkyl ether, apolyoxyalkylenealkylphenol, a polyoxyalkylene alkyl ester, the sorbitolester of polyoxyalkylene, polyethylene glycol, polypropylene glycol, anethylene oxide additive of diethylene glycol trimethylnonanol, andnonionic surfactants of polyester type, and also mixtures.

In addition, the solvents and dispersions may be combined with ironoxide suitable for use with cosmetic products, or a similar pigment, andalso zinc oxide, titanium oxide, silicon oxide, mica, talc or similarmineral oxides in powder form. In the dispersion, a mean particlediameter of the polymer of vinyl type may be within a range of between0.001 and 100 microns and preferably between 0.01 and 50 microns. Thereason for this is that, outside the recommended range, a cosmeticproduct mixed with the emulsion will not have a nice enough feel on theskin or to the touch, or sufficient spreading properties or a pleasantfeel.

A vinyl polymer contained in the dispersion or the solution may have aconcentration in the range between 0.1% and 95% by weight and preferablybetween 5% and 85% by weight. However, to facilitate the handling andthe preparation of the mixture, the range should preferably be between10% and 75% by weight.

According to one preferred mode, a vinyl polymer that is suitable foruse in the invention may be one of the polymers described in theexamples of patent application EP 0 963 751.

According to one preferred embodiment, a vinyl polymer grafted with acarbosiloxane dendrimer may be the product of polymerization of:

(A) from 0.1 to 99 parts by weight of one or more acrylate ormethacrylate monomers; and

(B) from 100 to 0.1 part by weight of an acrylate or methacrylatemonomer of atris[tri(trimethylsiloxy)silylethyldimethylsiloxy]silylpropylcarbosiloxane dendrimer.

According to one embodiment, a vinyl polymer containing at least onecarbosiloxane dendrimer-based unit may comprise atris[tri(trimethylsiloxy)silylethyldimethylsiloxy]sil-ylpropylcarbosiloxane dendrimer-based unit corresponding to one of the formulae:

According to one preferred mode, a vinyl polymer containing at least onecarbosiloxane dendrimer-based unit used in the invention comprises atleast one butyl acrylate monomer.

According to one embodiment, a vinyl polymer may also comprise at leastone fluoro organic group. A fluoro vinyl polymer may be one of thepolymers described in the examples of patent application WO 03/045 337.

According to one preferred embodiment, a vinyl polymer grafted in thesense of the present invention may be conveyed in an oil or a mixture ofoils, which are preferably volatile, chosen in particular from siliconeoils and hydrocarbon-based oils, and mixtures thereof.

According to one particular embodiment, a silicone oil that is suitablefor use in the invention may be cyclopentasiloxane.

According to another particular embodiment, a hydrocarbon-based oil thatis suitable for use in the invention may be isododecane.

Vinyl polymers grafted with at least one carbosiloxane dendrimer-basedunit that may be particularly suitable for use in the present inventionare the polymers sold under the names TIB 4-100, TIB 4-101, TIB 4-120,TIB 4-130, TIB 4-200, FA 4002 ID (TIB 4-202), TIB 4-220 and FA 4001 CM(TIB 4-230) by the company Dow Corning. The polymers sold under thenames FA 4002 ID (TIB 4-202) and FA 4001 CM (TIB 4-230) by the companyDow Corning will preferably be used.

Preferably, the vinyl polymer grafted with at least one carbosiloxanedendrimer-based unit that may be used in a composition of the inventionis an acrylate/polytrimethyl siloxymethacrylate copolymer, especiallythe product sold in isododecane under the name Dow Corning FA 4002 IDSilicone Acrylate by the company Dow Corning.

Silicone Acrylate Copolymers

According to one particular embodiment, a composition used according tothe invention may comprise, as hydrophobic film-forming polymer, atleast one copolymer comprising carboxylate groups andpolydimethylsiloxane groups.

In the present patent application, the expression “copolymer comprisingcarboxylate groups and polydimethylsiloxane groups” means a copolymerobtained from (a) one or more carboxylic (acid or ester) monomers, and(b) one or more polydimethylsiloxane (PDMS) chains.

In the present patent application, the term “carboxylic monomer” meansboth carboxylic acid monomers and carboxylic acid ester monomers. Thus,the monomer (a) may be chosen, for example, from acrylic acid,methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonicacid, esters thereof and mixtures of these monomers. Esters that may bementioned include the following monomers: acrylate, methacrylate,maleate, fumarate, itaconate and/or crotonate. According to onepreferred embodiment of the invention, the monomers in ester form aremore particularly chosen from linear or branched, preferably C₁-C₂₄ andbetter still C₁-C₂₂ alkyl acrylates and methacrylates, the alkyl radicalpreferably being chosen from methyl, ethyl, stearyl, butyl and2-ethylhexyl radicals, and mixtures thereof.

Thus, according to one particular embodiment of the invention, thecopolymer comprises as carboxylate groups at least one group chosen fromacrylic acid and methacrylic acid, and methyl, ethyl, stearyl, butyl or2-ethylhexyl acrylate or methacrylate, and mixtures thereof.

In the present patent application, the term “polydimethylsiloxanes”(also known as organopolysiloxanes and abbreviated as PDMS) denotes, inaccordance with what is generally accepted, any organosilicon polymer oroligomer of linear structure, of variable molecular weight, obtained bypolymerization and/or polycondensation of suitably functionalizedsilanes, and consisting essentially of a repetition of main units inwhich the silicon atoms are linked together via oxygen atoms (siloxanebond ≡Si—O-Si≡), comprising trimethyl radicals directly linked via acarbon atom to the said silicon atoms. The PDMS chains that may be usedto obtain the copolymer used according to the invention comprise atleast one polymerizable radical group, preferably located on at leastone of the ends of the chain, i.e. the PDMS may contain, for example, apolymerizable radical group on the two ends of the chain or onepolymerizable radical group on one end of the chain and onetrimethylsilyl end group on the other end of the chain. Theradical-polymerizable group may especially be an acrylic or methacrylicgroup, in particular a group CH₂═CR₁—CO—O—R₂, in which R₁ represents ahydrogen or a methyl group, and R₂ represents —CH₂—, —(CH₂)_(n)— withn=3, 5, 8 or 10, —CH₂—CH(CH₃)—CH₂—, —CH₂—CH₂—O—CH₂—CH₂—,—CH₂—CH₂—O—CH₂—CH₂—CH(CH₃)—CH₂— or —CH₂—CH₂—O—CH₂ CH₂—O—CH₂—CH₂—CH₂—.

The copolymers used in the composition of the invention are generallyobtained according to the usual methods of polymerization and grafting,for example by free-radical polymerization (A) of a PDMS comprising atleast one polymerizable radical group (for example on one of the ends ofthe chain or on both ends) and (B) of at least one carboxylic monomer,as described, for example, in documents U.S. Pat. No. 5,061,481 and U.S.Pat. No. 5,219,560.

The copolymers obtained generally have a molecular weight ranging fromabout 3000 to 200 000 and preferably from about 5000 to 100 000.

The copolymer used in the composition of the invention may be in itsnative form or in dispersed form in a solvent such as lower alcoholscontaining from 2 to 8 carbon atoms, for instance isopropyl alcohol, oroils, for instance volatile silicone oils (for examplecyclopentasiloxane).

As copolymers that may be used in the composition of the invention,mention may be made, for example, of copolymers of acrylic acid and ofstearyl acrylate containing polydimethylsiloxane grafts, copolymers ofstearyl methacrylate containing polydimethylsiloxane grafts, copolymersof acrylic acid and of stearyl methacrylate containingpolydimethylsiloxane grafts, copolymers of methyl methacrylate, butylmethacrylate, 2-ethylhexyl acrylate and stearyl methacrylate containingpolydimethylsiloxane grafts. As copolymers that may be used in thecomposition of the invention, mention may be made in particular of thecopolymers sold by the company Shin-Etsu under the names KP-561 (CTFAname: acrylates/dimethicone), KP-541 in which the copolymer is dispersedat 60% by weight in isopropyl alcohol (CTFA name: acrylates/dimethiconeand isopropyl alcohol), and KP-545 in which the copolymer is dispersedat 30% in cyclopentasiloxane (CTFA name: acrylates/dimethicone andcyclopentasiloxane). According to one preferred embodiment of theinvention, KP561 is preferably used; this copolymer is not dispersed ina solvent, but is in waxy form, its melting point being about 30° C.

Mention may also be made of the grafted copolymer of polyacrylic acidand dimethylpolysiloxane dissolved in isododecane, sold by the companyShin-Etsu under the is name KP-550.

A cosmetic makeup and/or care composition according to the inventionalso comprises a cosmetically acceptable medium that may comprise theusual ingredients, as a function of the intended use of the composition.

Filler

The composition according to the invention may also comprise at leastone organic or inorganic filler.

For example, a composition may comprise from 0.01% to 35% by weight andpreferably from 0.1% to 20% by weight of filler(s) relative to its totalweight.

Illustrations of these fillers that may be mentioned include talc, mica,silica, kaolin, calcium carbonate, barium sulfate, Nylon (especiallyOrgasol) powder and polyethylene powder, Teflon, starch, boron nitride,copolymer microspheres such as Expancel (Nobel Industrie) and siliconeresin microbeads (for example Tospearls from Toshiba); and also mixturesthereof.

According to one embodiment variant, a composition according to theinvention contains at least one filler that is capable of absorbing anoil.

In particular, a composition according to the invention comprises atleast one filler with capacity for absorbing and/or adsorbing an oil ora liquid fatty substance, for instance sebum (from the skin).

This oil-absorbing filler may also advantageously have a BET specificsurface area of greater than or equal to 300 m²/g, preferably greaterthan 500 m²/g and preferentially greater than 600 m²/g, and especiallyless than 1500 m²/g.

The BET specific surface area is determined according to the BET(Brunauer-Emmet-Teller) method described in the Journal of the AmericanChemical Society, vol. 60, page 309, February 1938 and corresponding tothe international standard ISO 5794/1 (appendix D). The BET specificsurface area corresponds to the total specific surface area (thusincluding micropores) of the powder.

The filler under consideration according to the invention is thuscharacterized in that it has an oil uptake of greater than or equal to 1ml/g, especially ranging from 1 ml/g to 20 ml/g, or even ranging from1.5 ml/g to 15 ml/g. It preferably has an oil uptake of greater than orequal to 2 ml/g, especially ranging from 2 ml/g to 20 ml/g, or evenranging from 2 ml/g to 15 ml/g.

This oil uptake, which corresponds to the amount of oil absorbed and/oradsorbed by the filler, may be characterized by measuring the wet pointaccording to the method described below.

Method for Measuring the Oil Uptake of a Filler:

The oil uptake of a powder is measured according to the method fordetermining the oil uptake of a powder are described in standard NF T30-022. It corresponds to the amount of oil adsorbed onto the availablesurface of the pulverulent material, by measuring the wet point.

An amount m (in grams) of powder of between about 0.5 g and 5 g (theamount depends on the density of the powder) is placed on a glass plateand isononyl isononanoate is then added dropwise.

After addition of 4 to 5 drops of isononyl isononanoate, the isononylisononanoate is incorporated into the filler using a spatula, andaddition of the isononyl isononanoate is continued until a conglomerateof isononyl isononanoate and powder has formed. At this point, theisononyl isononanoate is added one drop at a time and the mixture isthen triturated with the spatula. The addition of isononyl isononanoateis stopped when a firm, smooth paste is obtained. This paste must beable to be spread on the glass plate without cracking or forming lumps.The volume Vs (expressed in ml) of isononyl isononanoate used is thennoted.

The oil uptake corresponds to the ratio Vs/m.

This oil-absorbing filler may be a mineral powder or an organic powder;it may be chosen from silica, polyamide (Nylon®) powders, acrylicpolymer powders, especially polymethyl methacrylate powder, polymethylmethacrylate/ethylene glycol dimethacrylate powder polyallylmethacrylate/ethylene glycol dimethacrylate powder or ethylene glycoldimethacrylate/lauryl methacrylate copolymer powder; powders of siliconeelastomers obtained especially by polymerization of organopolysiloxanecontaining at least two hydrogen atoms each bonded to a silicon atom andof an organopolysiloxane comprising at least two ethylenicallyunsaturated groups (especially two vinyl groups) in the presence of aplatinum catalyst.

The oil-absorbing filler may be a powder coated with a hydrophobictreatment agent.

Examples of fillers with an oil uptake of greater than or equal to 1.5ml/g are described below, with their oil uptake value measured accordingto the protocol defined previously.

Silica powders that may be mentioned include:

-   -   porous silica microspheres, especially those sold under the        names Sunsphere® H53 and Sunsphere® H33 (oil uptake equal to        3.70 ml/g) by the company Asahi Glass; MSS-500-3H by the company        Kobo; Silica Beads SB-700 by the company Miyoshi,    -   polydimethylsiloxane-coated amorphous silica microspheres,        especially those sold under the name SA Sunsphere® H33 (oil        uptake equal to 2.43 ml/g),    -   silica silylate powders, especially those sold under the name        Dow Corning VM-2270 Aerogel Fine Particles by the company Dow        Corning (oil uptake equal to 10.40 ml/g),    -   amorphous hollow silica particles, especially those sold under        the name Silica Shells by the company Kobo (oil uptake equal to        5.50 ml/g),    -   precipitated silica powders surface-treated with a mineral wax,        such as precipitated silica treated with a polyethylene wax, and        especially those sold under the name Acematt OR 412 by the        company Evonik-Degussa (oil uptake equal to 3.98 ml/g).

Acrylic polymer powders that may be mentioned include:

-   -   porous polymethyl methacrylate/ethylene glycol dimethacrylate        spheres sold under the name Microsponge 5640 by the company        Cardinal Health Technologies (oil uptake equal to 1.55 ml/g),        Ganzpearl® GMP-0820 by the company Ganz Chemical,    -   ethylene glycol dimethacrylate/lauryl methacrylate copolymer        powders, especially those sold under the name Polytrap® 6603        from the company Dow Corning (oil uptake equal to 6.56 ml/g),    -   polymethyl methacrylate powders sold under the name Covabead®        LH85 by the company Wackherr,    -   polyallyl methacrylate/ethylene glycol dimethacrylate powders        sold under the names Polypore® L200 and Polypore® E200 by the        company Amcol.

Polyamide powders that may be mentioned include:

-   -   the nylon powder sold under the name Orgasol® 4000 by the        company Atochem,    -   nylon-6 powder, especially the product sold under the name        Pomp610 by the company UBE Industries (oil uptake equal to 2.02        ml/g).

A perlite powder that may especially be mentioned is the product soldunder the name Optimat 1430 OR by the company World Minerals (oil uptakeequal to 2.4 ml/g).

A magnesium carbonate powder that may especially be mentioned is theproduct sold under the name Tipo Carbomagel by the company Buschle &Lepper uptake equal to 2.14 ml/g).

The oil-absorbing filler that is particularly preferred is a silicapowder and more particularly a silica powder with an oil uptake at leastequal to 3.70 ml/g, and especially the products sold under the nameSunsphere® H33 by the company Asahi Glass and under the name Dow CorningVM-2270 Aerogel Fine Particles by the company Dow Corning.

The filler(s) that are especially capable of absorbing an oil may bepresent in a composition according to the invention in a content rangingfrom 0.5% to 40% by weight, preferably ranging from 1% to 20% by weightand preferentially ranging from 1% to 15% by weight relative to thetotal weight of the composition.

A composition according to the invention may use at least one filler andat least one supramolecular polymer in a polymer(s)/oil-absorbingfiller(s) weight ratio of greater than 1, preferably greater than 1.5and better still greater than 2.

According to one embodiment variant, a composition according to theinvention contains at least one filler with an oil uptake of greaterthan or equal to 1.5 ml/g.

Silicone Filler

According to another embodiment variant, a composition according to theinvention also contains at least one silicone filler.

The silicone filler may be chosen from:

-   -   organopolysiloxane powders coated with silicone resin; and    -   polymethylsilsesquioxane powders,

and a mixture thereof.

The organopolysiloxane powder may especially be coated withsilsesquioxane resin, as described, for example, in patent U.S. Pat. No.5,538,793. Such elastomeric powders are sold under the names KSP-100,KSP-101, KSP-102, KSP-103, KSP-104 and KSP-105 by the company Shin-Etsu,and have the INCI name: vinyl dimethicone/methicone silsesquioxanecrosspolymer.

Polymethylsilsesquioxane powders that may especially be mentionedinclude silicone resin microbeads, such as those sold under the nameTospearl by the company Momentive Performance Materials, and especiallyunder the reference Tospearl 145 A; and mixtures thereof

Dyestuff(s)

Preferably, a composition for making up and/or caring for the skinand/or the lips according to the invention comprises at least onedyestuff, in particular at least one pulverulent dyestuff.

The dyestuff is especially chosen from organic or mineral dyestuffs,especially such as the pigments or nacres conventionally used incosmetic compositions, liposoluble or water-soluble dyes, materials witha specific optical effect, and mixtures thereof.

The term “pigments” should be understood as meaning white or coloured,mineral or organic particles, which are insoluble in an aqueous solutionand which are intended to colour and/or opacify the resulting film.

These pigments may be in the form of powder or of pigmentary paste. Theymay be coated or uncoated.

As mineral pigments that may be used in the invention, mention may bemade of titanium oxide, zirconium oxide or cerium oxide, and also zincoxide, iron oxide or chromium oxide, ferric blue, manganese violet,ultramarine blue and chromium hydrate. In particular, the mineralpigments are chosen from iron oxides and titanium oxides, and mixturesthereof.

Among the organic pigments that may be used in the invention, mentionmay be made of carbon black, pigments of D&C type, lakes based oncochineal carmine or on barium, strontium, calcium or aluminium, oralternatively the diketopyrrolopyrroles (DPP) described in documentsEP-A-542 669, EP-A-787 730, EP-A-787 731 and WO-A-96/08537.

The term “lake” means dyes adsorbed onto insoluble particles, theassembly thus obtained remaining insoluble during use.

The pigments may also be in the form of composite pigments as describedin patent EP 1 184 426. These composite pigments may be especiallycomposed of particles comprising a mineral core, at least one binder forbinding the organic pigments to the core, and at least one organicpigment at least partially covering the core.

The term “nacres” should be understood as meaning iridescent ornon-iridescent coloured particles of any form, especially produced bycertain molluscs in their shell, or else synthesized, and which have acolour effect by optical interference.

The nacres may be chosen from nacreous pigments such as titanium micacoated with an iron oxide, titanium mica coated with bismuthoxychloride, titanium mica coated with chromium oxide, titanium micacoated with an organic dye and also nacreous pigments based on bismuthoxychloride. They may also be mica particles at the surface of which aresuperposed at least two successive layers of metal oxides and/or oforganic dyestuffs.

Examples of nacres that may also be mentioned include natural micacoated with titanium oxide, with iron oxide, with natural pigment orwith bismuth oxychloride. Among the nacres available on the market,mention may be made of the nacres

Timica, Flamenco and Duochrome (based on mica) sold by the companyEngelhard, the Timiron nacres sold by the company Merck, the Prestigemica-based nacres, sold by the company Eckart, and the Sunshinesynthetic mica-based nacres, sold by the company Sun Chemical.

The nacres may more particularly have a yellow, pink, red, bronze,orange, brown, gold and/or coppery colour or tint.

As illustrations of nacres that may be used in the context of thepresent invention, mention may be made especially of the gold-colourednacres sold especially by the company Engelhard under the name Brilliantgold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacressold especially by the company Merck under the name Bronze fine (17384)(Colorona) and Bronze (17353) (Colorona) and by the company Engelhardunder the name Super bronze (Cloisonne); the orange nacres soldespecially by the company Engelhard under the name Orange 363C(Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck underthe name Passion orange (Colorona) and Matte orange (17449) (Microna);the brown nacres sold especially by the company Engelhard under the nameNu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); thenacres with a copper tint sold especially by the company Engelhard underthe name Copper 340A (Timica); the nacres with a red tint soldespecially by the company Merck under the name Sienna fine (17386)(Colorona); the nacres with a yellow tint sold especially by the companyEngelhard under the name Yellow (4502) (Chromalite); the red nacres witha gold tint sold especially by the company Engelhard under the nameSunstone G012 (Gemtone); the pink nacres sold especially by the companyEngelhard under the name Tan opale G005 (Gemtone); the black nacres witha gold tint sold especially by the company Engelhard under the name Nuantique bronze 240 AB (Timica), the blue nacres sold especially by thecompany Merck under the name Matte blue (17433) (Microna), the whitenacres with a silvery tint sold especially by the company Merck underthe name Xirona Silver, and the golden-green pink-orange nacres soldespecially by the company Merck under the name Indian summer (Xirona),and mixtures thereof.

The cosmetic composition according to the invention may also comprisewater-soluble or liposoluble dyes. The term “dyes” should be understoodas meaning compounds that are generally organic, which are soluble infatty substances such as oils or in an aqueous-alcoholic phase. Theliposoluble dyes are, for example, Sudan red, DC Red 17, DC Green 6,β-carotene, Sudan brown, DC Yellow 11, DC Violet 2, DC Orange 5 andquinoline yellow. The water-soluble dyes are, for example, beetrootjuice and caramel.

The cosmetic composition according to the invention may also contain atleast one material with a specific optical effect.

This effect is different from a simple conventional hue effect, i.e. aunified and stabilized effect as produced by standard dyestuffs, forinstance monochromatic pigments. For the purposes of the invention, theterm “stabilized” means lacking an effect of variability of the colouras a function of the angle of observation or alternatively in responseto a temperature change.

For example, this material may be chosen from particles with a metallictint, goniochromatic colouring agents, diffracting pigments,thermochromic agents, optical brighteners, and also fibres, especiallyinterference fibres. Needless to say, these various materials may becombined so as to afford the simultaneous manifestation of two effects,or even of a novel effect in accordance with the invention.

The particles with a metallic tint that may be used in the invention arechosen in particular from:

-   -   particles of at least one metal and/or of at least one metal        derivative,    -   particles comprising a mono-material or multi-material organic        or mineral substrate, at least partially coated with at least        one coat with a metallic tint comprising at least one metal        and/or at least one metal derivative, and    -   mixtures of the said particles.

Among the metals that may be present in the said particles, mention maybe made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt,Va, Rb, W, Zn, Ge, Te and Se, and mixtures or alloys thereof. Ag, Au,Cu, Al, Zn, Ni, Mo and Cr and mixtures or alloys thereof (for examplebronzes and brasses) are preferred metals.

Illustrations of these particles that may be mentioned include aluminiumparticles, such as those sold under the names Starbrite 1200 EAC® by thecompany Siberline and Metalure® by the company Eckart.

Mention may also be made of copper metal powders or alloy mixtures suchas the reference 2844 sold by the company Radium Bronze, metallicpigments such as aluminium or bronze, such as those sold under the nameRotosafe 700 from the company Eckart, the silica-coated aluminiumparticles sold under the name Visionaire Bright Silver from the companyEckart and metal alloy particles, for instance the silica-coated bronze(alloy of copper and zinc) powders sold under the name Visionaire BrightNatural Gold from the company Eckart.

They may also be particles comprising a glass substrate, such as thosesold by the company Nippon Sheet Glass under the name MicroglassMetashine.

The goniochromatic colouring agent may be chosen, for example, frominterference multilayer structures and liquid-crystal colouring agents.

Examples of symmetrical interference multilayer structures that may beused in compositions produced in accordance with the invention are, forexample, the following structures: Al/SiO₂/Al/SiO₂/Al, pigments havingthis structure being sold by the company Dupont de Nemours;Cr/MgF₂/Al/MgF₂/Cr, pigments having this structure being sold under thename Chromaflair by the company Flex; MoS₂/SiO₂/Al/SiO₂/MoS₂;Fe₂O₃/SiO₂/Al/SiO₂/Fe₂O₃, and Fe₂O₃/SiO₂/Fe₂O₃/SiO₂/Fe₂O₃, pigmentshaving these structures being sold under the name Sicopearl by thecompany BASF; MoS₂/SiO₂/mica-oxide/SiO₂/MoS₂;Fe₂O₃/SiO₂/mica-oxide/SiO₂/Fe₂O₃; TiO₂/SiO₂/TiO₂ and TiO₂/Al₂O₃/TiO₂;SnO/TiO₂/SiO₂/TiO₂/SnO; Fe₂O₃/SiO₂/Fe₂O₃;SnO/mica/TiO₂/SiO₂/TiO₂/mica/SnO, pigments having these structures beingsold under the name Xirona by the company Merck (Darmstadt). By way ofexample, these pigments may be the pigments of silica/titanium oxide/tinoxide structure sold under the name Xirona Magic by the company Merck,the pigments of silica/brown iron oxide structure sold under the nameXirona Indian Summer by the company Merck and the pigments ofsilica/titanium oxide/mica/tin oxide structure sold under the nameXirona Caribbean Blue by the company Merck. Mention may also be made ofthe Infinite Colors pigments from the company Shiseido. Depending on thethickness and the nature of the various coats, different effects areobtained. Thus, with the Fe₂O₃/SiO₂/Al/SiO₂/Fe₂O₃ structure, the colourchanges from green-golden to red-grey for SiO₂ layers of 320 to 350 nm;from red to golden for SiO₂ layers of 380 to 400 nm; from violet togreen for SiO₂ layers of 410 to 420 nm; from copper to red for SiO₂layers of 430 to 440 nm.

Examples of pigments with a polymeric multilayer structure that may bementioned include those sold by the company 3M under the name ColorGlitter.

Examples of liquid-crystal goniochromatic particles that may be usedinclude those sold by the company Chenix and also the product sold underthe name Helicone® HC by the company Wacker.

Preferably, the amount of dyestuffs in a composition according to theinvention is between 0.01% and 40% by weight and especially between 0.1%and 30% by weight, or even between 1% and 20% by weight relative to thetotal weight of the composition.

Fatty Phase

A composition according to the invention may comprise a fatty phase,which may represent from 1% to 98% by weight, especially 5% to 95% byweight or even 10% to 90% by weight relative to the total weight of thecomposition. This fatty phase may comprise oils, waxes and/or pastycompounds and/or silicone compounds as defined below.

The oils, preferably silicone oils, and/or silicone compounds may bepresent in a proportion ranging from 0.1% to 60% by weight andpreferably from 0.5% to 40% by weight relative to the total weight ofthe composition.

Thus, a composition according to the invention may advantageouslycomprise one or more oils, which may be chosen especially fromhydrocarbon-based oils and fluoro oils, and mixtures thereof. The oilsmay be of animal, plant, mineral or synthetic origin.

The term “oil” means a water-immiscible non-aqueous compound that isliquid at room temperature (25° C.) and at atmospheric pressure (760mmHg).

The oils may be volatile or non-volatile.

For the purposes of the invention, the term “volatile oil” means any oilthat is capable of evaporating on contact with keratin materials in lessthan one hour, at room temperature and atmospheric pressure. Volatileoils preferably have a non-zero vapour pressure, at room temperature andatmospheric pressure, ranging from 0.13 Pa to 40 000 Pa, in particularfrom 1.3 Pa to 13 000 Pa and more particularly from 1.3 Pa to 1300 Pa.

The term “fluoro oil” means an oil comprising at least one fluorineatom.

The term “hydrocarbon-based oil” means an oil mainly containing hydrogenand carbon atoms.

The oils may optionally comprise oxygen, nitrogen, sulfur and/orphosphorus atoms, for example in the form of hydroxyl or acid radicals.

The volatile oils may be chosen from hydrocarbon-based oils containingfrom 8 to 16 carbon atoms, and especially C₈-C₁₆ branched alkanes (alsoknown as isoparaffins), for instance isododecane, isodecane andisohexadecane.

The volatile hydrocarbon-based oil may also be a linear volatile alkanecontaining 7 to 17 carbon atoms, in particular 9 to 15 carbon atoms andmore particularly 11 to 13 carbon atoms. Mention may be made especiallyof n-nonadecane, n-decane, n-undecane, n-dodecane, n-tridecane,n-tetradecane, n-pentadecane and n-hexadecane, and mixtures thereof.

Non-volatile oils that may especially be mentioned include:

-   -   hydrocarbon-based oils of animal origin,    -   hydrocarbon-based oils of plant origin, such as phytostearyl        esters, such as phytostearyl oleate, phytostearyl isostearate        and lauroyl/octyldodecyl/phytostearyl glutamate; triglycerides        formed from fatty acid esters of glycerol, in particular whose        fatty acids may have chain lengths ranging from C₄ to C₃₆ and        especially from C₁₈ to C₃₆, these oils possibly being linear or        branched, and saturated or unsaturated; these oils may        especially be heptanoic or octanoic triglycerides, shea oil,        alfalfa oil, poppy oil, pumpkin oil, millet oil, barley oil,        quinoa oil, rye oil, candlenut oil, passionflower oil, shea        butter oil, aloe oil, sweet almond oil, peach stone oil,        groundnut oil, argan oil, avocado oil, baobab oil, borage oil,        broccoli oil, calendula oil, camellina oil, carrot oil,        safflower oil, hemp oil, rapeseed oil, cottonseed oil, coconut        oil, marrow seed oil, wheatgerrn oil, jojoba oil, lily oil,        macadamia oil, corn oil, meadowfoam oil, St-John's wort oil,        monoi oil, hazelnut oil, apricot kernel oil, walnut oil, olive        oil, evening primrose oil, palm oil, blackcurrant pip oil, kiwi        seed oil, grape seed oil, pistachio oil, pumpkin oil, quinoa        oil, musk rose oil, sesame oil, soybean oil, sunflower oil,        castor oil and watermelon oil, and mixtures thereof, or        alternatively caprylic/capric acid triglycerides, such as those        sold by the company Stearineries Dubois or those sold under the        names Miglyol 810®, 812® and 818® by the company Dynamit Nobel,    -   synthetic ethers containing from 10 to 40 carbon atoms,    -   synthetic esters, for instance the oils of formula R₁COOR₂, in        which R₁ represents a linear or branched fatty acid residue        containing from 1 to 40 carbon atoms and R₂ represents a        hydrocarbon-based chain, which is especially branched,        containing from 1 to 40 carbon atoms, on condition that        R₁+R₂≧10. The esters may be chosen especially from fatty acid        esters of alcohols, for instance cetostearyl octanoate,        isopropyl alcohol esters, such as isopropyl myristate, isopropyl        palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl        stearate, isopropyl isostearate, isostearyl isostearate, octyl        stearate, hydroxylated esters, for instance isostearyl lactate,        octyl hydroxystearate, diisopropyl adipate, heptanoates, and        especially isostearyl heptanoate, alcohol or polyalcohol        octanoates, decanoates or ricinoleates, for instance propylene        glycol dioctanoate, cetyl octanoate, tridecyl octanoate,        2-ethylhexyl 4-diheptanoate, 2-ethylhexyl palmitate, alkyl        benzoates, polyethylene glycol diheptanoate, propylene glycol        2-diethylhexanoate, and mixtures thereof, C₁₂-C₁₅ alcohol        benzoates, hexyl laurate, neopentanoic acid esters, for instance        isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl        neopentanoate, octyldodecyl neopentanoate, isononanoic acid        esters, for instance isononyl isononanoate, isotridecyl        isononanoate, octyl isononanoate, hydroxylated esters, for        instance isostearyl lactate and diisostearyl malate, polyol        esters and pentaerythritol esters, for instance        dipentaerythrityl tetrahydroxystearate/tetraisostearate,    -   esters of diol dimers and of diacid dimers,    -   copolymers of dial dimer and of diacid dimer and esters thereof,        such as dilinoleyl diol dimer/dilinoleic dimer copolymers, and        esters thereof,    -   copolymers of polyols and of diacid dimers, and esters thereof,    -   fatty alcohols that are liquid at room temperature, with a        branched and/or unsaturated carbon-based chain containing from        12 to 26 carbon atoms, for instance 2-octyldodecanol, isostearyl        alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and        2-undecylpentadecanol,    -   C₁₂-C₂₂ higher fatty acids, such as oleic acid, linoleic acid        and linolenic acid, and mixtures thereof,    -   dialkyl carbonates, the two alkyl chains possibly being        identical or different, such as dicaprylyl carbonate,    -   oils with a molar mass of between about 400 and about 10 000        g/mol, in particular about 650 to about 10 000 g/mol, in        particular from about 750 to about 7500 g/mol and more        particularly ranging from about 1000 to about 5000 g/mol;        mention may be made especially, alone or as a mixture, of (i)        lipophilic polymers such as polybutylenes, polyisobutylenes, for        example hydrogenated, polydecenes and hydrogenated polydecenes,        vinylpyrrolidone copolymers, such as the        vinylpyrrolidone/1-hexadecene copolymer, and        polyvinylpyrrolidone (PVP) copolymers, such as the copolymers of        a C₂-C₃₀ alkene, such as C₃-C₂₂, and combinations thereof; (ii)        linear fatty acid esters containing a total carbon number        ranging from 35 to 70, for instance pentaerythrityl        tetrapelargonate; (iii) hydroxylated esters such as        polyglyceryl-2 triisostearate; (iv) aromatic esters such as        tridecyl trimellitate; (v) esters of fatty alcohols or of        branched C₂₄-C₂₈ fatty acids, such as those described in patent        U.S. Pat. No. 6,491,927 and pentaerythritol esters, and        especially triisoarachidyl citrate, pentaerythrityl        tetraisononanoate, glyceryl triisostearate, glyceryl        2-tridecyltetradecanoate, pentaerythrityl tetraisostearate,        poly(2-glyceryl) tetraisostearate or pentaerythrityl        2-tetradecyltetradecanoate; (vi) diol dimer esters and        polyesters, such as esters of diol dimer and of fatty acid, and        esters of diol dimer and of diacid.

In particular, one or more oils according to the invention may bepresent in a composition according to the invention in a content rangingfrom 1% to 90% by weight, preferably ranging from 2% to 75% by weight oreven from 3% to 60% by weight relative to the total weight of thecomposition.

It is understood that this weight percentage of oil takes into accountthe weight of oil used for the formulation of the associatedsupramolecular polymer, if present.

Silicone Compound

A composition according to the invention may also comprise at least onesilicone compound with a viscosity of less than 10 000 000 cSt at 25° C.Such a compound is advantageously chosen from silicone gums, volatilesilicone oils and non-volatile silicone oils.

In particular, the silicone compound under consideration according tothe invention may be a silicone oil with a viscosity of between 3centistokes (cSt) (3×10⁻⁶ m²/s) and 800 000 centistokes (cSt) (800000×10⁻⁶ m²/s),

Preferably, the silicone compound under consideration according to theinvention may be a non-volatile silicone oil with a viscosity of between9 centistokes (cSt) (9×10⁻⁶ m²/s) and 600 000 centistokes (cSt) (600000×10⁻⁶ m²/s).

Silicone Oils

The term “oil” means a water-immiscible non-aqueous compound that isliquid at room temperature (25° C.) and at atmospheric pressure (760mmHg).

For the purposes of the present invention, the term “silicone oil” meansan oil comprising at least one silicon atom, and especially at least oneSi—O group.

In particular, the volatile or non-volatile silicone oils that may beused in the invention preferably have a viscosity at 25° C. of less than800 000 cSt, preferably less than or equal to 600 000 cSt and preferablyless than or equal to 500 000 cSt. The viscosity of these silicone oilsmay be measured according to standard ASTM D-445,

As emerges from the foregoing text, a composition according to theinvention and/or under consideration according to a process of theinvention contains at least one silicone oil other thancyclopentasiloxane. Such an oil, also known asdecamethylcyclopentasiloxane, is especially sold under the name DC-245by the company Dow Corning or Mirasil CM 5.

Needless to say, a composition according to the invention or underconsideration according to a process of the invention may contain amixture of silicone oils formed only partly from such an oil.

The silicone oils that may be used according to the invention may bevolatile and/or non-volatile.

Thus, a composition according to the invention or under considerationaccording to a process of the invention may contain a mixture ofvolatile and non-volatile silicone oil.

The term “volatile oil” means an oil that can evaporate on contact withthe skin in less than one hour, at room temperature (25° C.) andatmospheric pressure. The volatile oil is a volatile cosmetic oil, whichis liquid at room temperature, especially having a non-zero vapourpressure, at room temperature and atmospheric pressure, in particularhaving a vapour pressure ranging from 0.13 Pa to 40 000 Pa (10⁻³ to 300mmHg), preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg)and preferentially ranging from 1.3 Pa to 1300 Pa (0.1 to 10 mmHg).

The term “non-volatile oil” means an oil whose vapour pressure at roomtemperature and atmospheric pressure is non-zero and less than 0.02 mmHg(2.66 Pa) and better still less than 10⁻³ mmHg (0.13 Pa).

Volatile Silicone Oils

According to a first embodiment, the compositions according to theinvention comprise at least one volatile silicone oil.

The volatile silicone oils that may be used in the invention may bechosen from silicone oils especially having a viscosity of 8 centistokes(cSt) (8×10⁻⁶ m²/s).

Furthermore, the volatile silicone oil that may be used in the inventionmay preferably be chosen from silicone oils with a flash point rangingfrom 40° C. to 102° C., preferably with a flash point of greater than55° C. and less than or equal to 95° C., and preferentially ranging from65° C. to 95° C.

Volatile silicone oils that may be mentioned include:

-   -   volatile linear or cyclic silicone oils, especially those with a        viscosity ≦8 centistokes (cSt) (8×10⁻⁶ m²/s at 25° C.), and        especially containing from 2 to 10 silicon atoms and in        particular from 2 to 7 silicon atoms, these silicones optionally        comprising alkyl or alkoxy groups containing from 1 to 10 carbon        atoms.

More particularly, the volatile silicone oils are non-cyclic and arechosen in particular from:

-   -   the non-cyclic linear silicones of formula (I):

R₃SiO—(R₂SiO)_(n)-SiR₃  (I)

in which R, which may be identical or different, denotes:

-   -   a saturated or unsaturated hydrocarbon-based radical, containing        from 1 to 10 carbon atoms and preferably from 1 to 6 carbon        atoms, optionally substituted with one or more fluorine atoms or        with one or more hydroxyl groups, or    -   a hydroxyl group, one of the radicals R possibly being a phenyl        group, n is an integer ranging from 0 to 8, preferably ranging        from 2 to 6 and better still ranging from 3 to 5, the silicone        compound of formula (I) containing not more than 15 carbon        atoms,    -   the branched silicones of formula (II) or (III) below:

R₃SiO—[(R₃SiO)RSiO]—(R₂SiO)_(x)—SiR₃  (II)

[R₃SiO]4Si  (III)

in which R, which may be identical or different, denotes:

-   -   a saturated or unsaturated hydrocarbon-based radical, containing        from 1 to 10 carbon atoms, optionally substituted with one or        more fluorine atoms or with one or more hydroxyl groups, or    -   a hydroxyl group, one of the radicals R possibly being a phenyl        group, x is an integer ranging from 0 to 8, the silicone        compound of formula (II) or (III) containing not more than 15        carbon atoms.

Preferably, for the compounds of formulae (I), (II) and (III), the ratiobetween the number of carbon atoms and the number of silicon atoms isbetween 2.25 and 4.33.

The silicones of formulae (I) to (III) may be prepared according to theknown processes for synthesizing silicone compounds.

Among the silicones of formula (I) that may be mentioned are:

-   -   the following disiloxanes: hexamethyldisiloxane (surface        tension=15.9 mN/m), sold especially under the name DC 200        Fluid 0. 65 cSt by the company Dow Corning,        1,3-di-tert-butyl-1,1,3,3-tetramethyldisiloxane;        1,3-dipropyl-1,1,3,3-tetramethyldisiloxane;        heptylpentamethyldisiloxane; 1,1,1-triethyl-3,3,3        trimethyldisiloxane; hexaethyldisiloxane;        1,1,3,3-tetramethyl-1,3-bis(2-methylpropyl)disiloxane;        pentamethyloctyldisiloxane;        1,1,1-trimethyl-3,3,3-tris(1-methylethyl)disiloxane;        1-butyl-3-ethyl-1,1,3-trimethyl-3-propyldisiloxane;        pentamethylpentyldisiloxane;        1-butyl-1,1,3,3-tetramethyl-3-(1-methylethyl)disiloxane;        1,1,3,3-tetramethyl-1,3-bis(1-methylpropyl)disiloxane;        1,1,3-triethyl-1,3,3-tripropyldisiloxane;        (3,3-dimethylbutyl)pentamethyldisiloxane;        (3-methylbutyl)pentamethyldisiloxane;        (3-methylpentyl)pentamethyldisiloxane;        1,1,1-triethyl-3,3-dimethyl-3-propyldisiloxane;        1-(1,1-dimethylethyl)-1,1,3,3,3-pentamethyldisiloxane;        1,1,1-trimethyl-3,3,3-tripropyldisiloxane;        1,3-dimethyl-1,1,3,3-tetrakis(1-methylethyl)disiloxane;        1,1-dibutyl-1,3,3,3-tetramethyldisiloxane;        1,1,3,3-tetramethyl-1,3-bis(1-methylethyl)disiloxane;        1,1,1,3-tetramethyl-3,3-bis(1methylethyl)disiloxane;        1,1,1,3-tetramethyl-3,3-dipropyldisiloxane;        1,1,3,3-tetramethyl-1,3-bis(3-methylbutyl)disiloxane;        butylpentamethyldisiloxane; pentaethylmethyldisiloxane;        1,1,3,3-tetramethyl-1,3-dipentyldisiloxane;        1,3-dimethyl-1,1,3,3-tetrapropyldisiloxane;        1,1,1,3-tetraethyl-3,3-dimethyldisiloxane;        1,1,1-triethyl-3,3,3-tripropyldisiloxane;        1,3-dibutyl-1,1,3,3-tetramethyldisiloxane and        hexylpentamethyldisiloxane;    -   the following trisiloxanes: octamethyltrisiloxane (surface        tension=17.4 mN/m), sold especially under the name DC 200 Fluid        1 cSt by the company Dow Corning,        3-pentyl-1,1,1,3,5,5,5-heptamethyltrisiloxane;        1-hexyl-1,1,3,3,5,5,5-heptamethyltrisiloxane;        1,1,1,3,3,5,5-heptamethyl5-octyltrisiloxane;        1,1,1,3,5,5,5-heptamethyl-3-octyltrisiloxane, sold especially        under the name Silsoft 034 by the company OSI;        1,1,1,3,5,5,5-heptamethyl-3-hexyltrisiloxane (surface        tension=20.5 mN/m), sold especially under the name DC 2-1731 by        the company Dow Corning;        1,1,3,3,5,5-hexamethyl-1,5-dipropyltrisiloxane;        3-(1-ethylbutyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane;        1,1,1,3,5,5,5-heptamethyl-3-(1-methylpentyl)trisiloxane;        hexamethyltrisiloxane;        1,1,1,3,5,5,5-heptamethyl-3-(1-methylpropyl)trisiloxane;        3-(1,1-dimethylethyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane;        1,1,1,5,5,5-hexamethyl-3,3-bis(1-methylethyl)trisiloxane;        1,1,1,3,3,5,5-hexamethyl-1,5-bis(1-methylpropyl)trisiloxane;        1,5-bis(1,1-dimethylethyl)-1,1,3,3,5,5-hexamethyltrisiloxane;        3-(3,3-dimethylbutyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane;        1,1,1,3,5,5,5-heptamethyl-3-(3-methylbutyl)trisiloxane;        1,1,1,3,5,5,5-heptamethyl-3-(3-methylpentyl)trisiloxane;        1,1,1,3,5,5,5-heptamethyl-3-(2-methylpropyl)trisiloxane;        1-butyl-1,1,3,3,5,5,5-heptamethyltrisiloxane;        1,1,1,3,5,5,5-heptamethyl-3-propyltrisiloxane;        3-isohexyl-1,1,1,3,5,5,5-heptamethyltrisiloxane;        1,3,5-triethyl-1,1,3,5,5-pentamethyltrisiloxane;        3-butyl-1,1,1,3,5,5,5-heptamethyltrisiloxane;        3-tert-pentyl-1,1,1,3,5,5,5-heptamethyltrisiloxane;        1,1,1,5,5,5-hexamethyl-3,3-dipropyltrisiloxane;        3,3-diethyl-1,1,1,5,5,5-hexamethyltrisiloxane;        1,5-dibutyl-1,1,3,3,5,5-hexamethyltrisiloxane;        1,1,1,5,5,5-hexaethyl-3,3-dimethyltrisiloxane;        3,3-dibutyl-1,1,1,5,5,5-hexamethyltrisiloxane;        3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane;        3-heptyl-1,1,1,3,5,5,5-heptamethyltrisiloxane and        1-ethyl-1,1,3,3,5,5,5-heptamethyltrisiloxane;    -   the following tetrasiloxanes: decamethyltetrasiloxane (surface        tension=18 mN/m), sold especially under the name DC 200 Fluid        1.5 cSt by the company Dow Corning;        1,1,3,3,5,5,7,7-octamethyl-1,7-dipropyltetrasiloxane;        1,1,1,3,3,5,7,7,7-nonamethyl-5-(1-methylethyl)tetrasiloxane;        1-butyl-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane;        3,5-diethyl-1,1,1,3,5,7,7,7-octamethyltetrasiloxane;        1,3,5,7-tetraethyl-1,1,3,5,7,7-hexamethyltetrasiloxane;        3,3,5,5-tetraethyl-1,1,1,7,7,7-hexamethyltetrasiloxane;        1,1,1,3,3,5,5,7,7-nonamethyl-7-phenyltetrasiloxane;        1,1,1,5,5,7,7,7-octamethyltetrasiloxane;        1,1,1,3,3,5,7,7,7-nonamethyl-5-phenyltetrasiloxane;    -   the following pentasiloxanes: dodecamethylpentasiloxane (surface        tension=18.7 mN/m), sold especially under the name DC 200 Fluid        2 cSt by the company Dow Corning;        1,1,3,3,5,5,7,7,9,9-decamethyl-1,9-dipropylpentasiloxane;        3,3,5,5,7,7-hexaethyl-1,1,1,9,9,9-hexamethylpentasiloxane;        1,1,1,3,3,5,7,7,9,9,9-undecamethyl-5-phenylpentasiloxane;        1-butyl-1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane;        3,3-diethyl-1,1,1,5,5,7,7,9,9,9-decamethylpentasiloxane;        1,3,5,7,9-pentaethyl-1,1,3,5,7,9,9-heptamethylpentasiloxane;        3,5,7-triethyl-1,1,1,3,5,7,9,9,9-nonamethylpentasiloxane and        1,1,1-triethyl-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane;    -   the following hexasiloxanes:        1-butyl-1,1,3,3,5,5,7,7,9,9,11,11,11-tridecamethylhexasiloxane;        3,5,7,9-tetraethyl-1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane        and tetradecamethylhexasiloxane;    -   hexadecamethylheptasiloxane;    -   octadecamethyloctasiloxane;    -   eicosamethylnonasiloxane.

Among the silicones of formula (II) that may be mentioned are:

-   -   the following tetrasiloxanes:        2-[3,3,3-trimethyl-1,1-bis[(trimethylsylil)oxy]disiloxanyl]ethyl;        1,1,1,5,5,5-hexamethyl-3-(2-methylpropyl)-3-[(trimethylsilyl)oxy]trisiloxane;        3-(1,1-dimethylethyl)-1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]trisiloxane;        3-butyl-1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]trisiloxane;        1,1,1,5,5,5-hexamethyl-3-propyl-3-[(trimethylsilyl)oxy]trisiloxane;        3-ethyl-1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]trisiloxane;        1,1,1-triethyl-3,5,5,5-tetramethyl-3-(trimethylsiloxy)trisiloxane;        3-methyl-1,1,1,5,5,5-hexamethyl-3-[trimethylsilyl)oxy]trisiloxane;        3-[(dimethylphenylsilyl)oxy]-1,1,1,3,5,5,5-heptamethyltrisiloxane;        1,1,1,5,5,5-hexamethyl-3-(2-methylpentyl)-3-[(trimethylsilyl)oxy]trisiloxane;        1,1,1,5,5,5-hexamethyl-3-(4-methylpentyl)-3-[(trimethylsilyl)oxy]trisiloxane;        3-hexyl-1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]trisiloxane        and        1,1,1,3,5,5,5-heptamethyl-3-[(trimethylsilyl)oxy]trisiloxane;    -   the following pentasiloxanes:        1,1,1,3,5,5,7,7,7-nonamethyl-3-(trimethylsiloxy)tetrasiloxane        and        1,1,1,3,3,7,7,7-octamethyl-5-phenyl-5-[(trimethylsilyl)oxy]tetrasiloxane;    -   the following hexasiloxane:        1,1,1,3,5,5,7,7,9,9,11,11,11-tridecamethyl-3-[(trimethylsilyl)oxy]hexasiloxane.

Among the silicones of formula (III), mention may be made of:

-   -   1,1,1,5,5,5-hexamethyl-3,3-bis(trimethylsiloxy)trisiloxane.

Use may also be made of other volatile silicone oils chosen from:

-   -   the following tetrasiloxanes:        2,2,8,8-tetramethyl-5-[(pentamethyldisiloxanyl)methyl]-3,7-dioxa-2,8-disilanonane;        2,2,5,8,8-pentamethyl-5-[(trimethylsilyl)methoxy]-4,6-dioxa-2,5,8-trisilanonane;        1,3-dimethyl-1,3-bis[(trimethylsilyl)methyl]-1,3-disiloxanediol;        3-ethyl-1,1,1,5,5,5-hexamethyl-3-[3-(trimethylsiloxy)propyl]trisiloxane        and        1,1,1,5,5,5-hexamethyl-3-phenyl-3-[(trimethylsilyl)oxy]trisiloxane        (Dow 556 Fluid);    -   the following pentasiloxanes:        2,2,7,7,9,9,11,11,16,16-decamethyl-3,8,10,15-tetraoxa-2,7,9,11,16-pentasilaheptadecane        and the tetrakis[(trimethylsilyl)methyl]ester of silicic acid;

the following hexasiloxanes:3,5-diethyl-1,1,1,7,7,7-hexamethyl-3,5-bis[(trimethylsilyl)oxy]tetrasiloxaneand1,1,1,3,5,7,7,7-octamethyl-3,5-bis[(trimethylsilyl)oxy]tetrasiloxane;

-   -   the heptasiloxane:        1,1,1,3,7,7,7-heptamethyl-3,5,5-tris[(trimethylsilyl)oxy]tetrasiloxane;    -   the following octasiloxanes:        1,1,1,3,5,5,9,9,9-nonamethyl-3,7,7-tris[(trimethylsilyl)oxy]pentasiloxane;        1,1,1,3,5,7,9,9,9-nonamethyl-3,5,7-tris[(trimethylsilyl)oxy]pentasiloxane        and        1,1,1,7,7,7-hexamethyl-3,3,5,5-tetrakis[(trimethylsilyl)oxy]tetrasiloxane.

Volatile silicone oils that may more particularly be mentioned includedecamethylcyclopentasiloxane sold especially under the name DC-245 bythe company Dow Corning, dodecamethylcyclohexasiloxane sold especiallyunder the name DC-246 by the company Dow Corning, octamethyltrisiloxanesold especially under the name DC-200 Fluid 1 cSt by the company DowCorning, decamethyltetrasiloxane sold especially under the name DC-200Fluid 1.5 cSt by the company Dow Corning and DC-200 Fluid 5 cSt sold bythe company Dow Corning, octamethylcyclotetrasiloxane,heptamethylhexyltrisiloxane, heptamethylethyltrisiloxane,heptamethyloctyltrisiloxane and dodecamethylpentasiloxane, and mixturesthereof.

It should be noted that, among the abovementioned oils, the linear oilsprove to be particularly advantageous.

Non-Volatile Silicone Oils

According to a second embodiment, the compositions according to theinvention comprise at least one non-volatile silicone oil.

The non-volatile silicone oils that may be used in the invention may bechosen from silicone oils with a viscosity at 25° C. of greater than orequal to 9 centistokes (cSt) (9×10⁻⁶ m²/s) and less than 800 000 cSt,preferably between 50 and 600 000 cSt and preferably between 100 and 500000 cSt. The viscosity of this silicone oil may be measured according tostandard ASTM D-445.

Among these silicone oils, two types of oil may be distinguished,according to whether or not they contain phenyl.

Representative examples of these non-volatile linear silicone oils thatmay be mentioned include polydimethylsiloxanes; alkyl dimethicones;vinyl methyl methicones; and also silicones modified with optionallyfluorinated aliphatic groups, or with functional groups such ashydroxyl, thiol and/or amine groups.

Thus, non-phenyl non-volatile silicone oils that may be mentionedinclude:

-   -   PDMSs comprising alkyl or alkoxy groups, which are pendent        and/or at the end of the silicone chain, these groups each        containing from 2 to 24 carbon atoms,    -   PDMSs comprising aliphatic groups, or functional groups such as        hydroxyl, thiol and/or amine groups,    -   polyalkylmethylsiloxanes optionally substituted with a        fluorinated group, such as        polymethyltrifluoropropyldimethylsiloxanes,    -   polyalkylmethylsiloxanes substituted with functional groups such        as hydroxyl, thiol and/or amine groups,    -   polysiloxanes modified with fatty acids, fatty alcohols or        polyoxyalkylenes, and mixtures thereof.

According to one embodiment, a composition according to the inventioncontains at least one non-phenyl linear silicone oil.

The non-phenyl linear silicone oil may be chosen especially from thesilicones of formula:

in which:

R₁, R₂, R₅ and R₆ are, together or separately, an alkyl radicalcontaining 1 to 6 carbon atoms,

R₃ and R₄ are, together or separately, an alkyl radical containing from1 to 6 carbon atoms, a vinyl radical, an amine radical or a hydroxylradical,

X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxylradical or an amine radical,

n and p are integers chosen so as to have a fluid compound.

As non-volatile silicone oils that may be used according to theinvention, mention may be made of those for which:

-   -   the substituents R₁ to R₆ and X represent a methyl group, and p        and n are such that the viscosity is 500 000 cSt, such as the        product sold under the name SE30 by the company General        Electric, the product sold under the name AK 500000 by the        company Wacker, the product sold under the name Mirasil DM 500        000 by the company Bluestar, and the product sold under the name        Dow Corning 200 Fluid 500 000 cSt by the company Dow Corning,    -   the substituents R₁ to R₆ and X represent a methyl group, and p        and n are such that the viscosity is 60 000 cSt, such as the        product sold under the name Dow Corning 200 Fluid 60000 CS by        the company Dow Corning, and the product sold under the name        Wacker Belsil DM 60 000 by the company Wacker,    -   the substituents R₁ to R₆ and X represent a methyl group, and p        and n are such that the viscosity is 350 cSt, such as the        product sold under the name Dow Corning 200 Fluid 350 CS by the        company Dow Corning,    -   the substituents R₁ to R₆ represent a methyl group, the group X        represents a hydroxyl group, and n and p are such that the        viscosity is 700 cSt, such as the product sold under the name        Baysilone Fluid T0.7 by the company Momentive.

According to one embodiment variant, a composition according to theinvention contains at least one phenyl silicone oil.

Representative examples of these non-volatile phenyl silicone oils thatmay be mentioned include:

-   -   the phenyl silicone oils corresponding to the following formula:

in which the groups R represent, independently of each other, a methylor a phenyl, with the proviso that at least one group R represents aphenyl. Preferably, in this formula, the phenyl silicone oil comprisesat least three phenyl groups, for example at least four, at least fiveor at least six.

-   -   the phenyl silicone oils corresponding to the following formula:

in which the groups R represent, independently of each other, a methylor a phenyl, with the proviso that at least one group R represents aphenyl. Preferably, in this formula, the said organopolysiloxanecomprises at least three phenyl groups, for example at least four or atleast five. Mixtures of the phenyl organopolysiloxanes describedpreviously may be used. Examples that may be mentioned include mixturesof triphenyl, tetraphenyl or pentaphenyl organo-polysiloxanes.

-   -   the phenyl silicone oils corresponding to the following formula:

in which Me represents methyl and Ph represents phenyl. Such a phenylsilicone is especially manufactured by Dow Corning under the referencePH-1555 HRI or Dow Corning 555 Cosmetic Fluid (chemical name:1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane; INCI name: trimethylpentaphenyl trisiloxane). The reference Dow Corning 554 Cosmetic Fluidmay also be used.

-   -   the phenyl silicone oils corresponding to the following formula:

in which Me represents methyl, y is between 1 and 1000 and X represents—CH₂—CH(CH₃)(Ph).

-   -   the phenyl silicone oils corresponding to formula (V) below:

in which Me is methyl and Ph is phenyl, OR′ represents a group —OSiMe₃and y is 0 or ranges between 1 and 1000, and z ranges between 1 and1000, such that compound (V) is a non-volatile oil.

According to a first embodiment, y ranges between 1 and 1000. Use may bemade, for example, of trimethyl siloxyphenyl dimethicone, soldespecially under the reference Belsil PDM 1000 sold by the companyWacker.

According to a second embodiment, y is equal to 0. Use may be made, forexample, of phenyl trimethylsiloxy trisiloxane, sold especially underthe reference Dow Corning 556 Cosmetic Grade Fluid.

-   -   the phenyl silicone oils corresponding to formula (VI) below,        and mixtures thereof:

in which:

-   -   R₁ to R₁₀, independently of each other, are saturated or        unsaturated, linear, cyclic or branched C₁-C₃₀ hydrocarbon-based        radicals,    -   m, n, p and q are, independently of each other, integers between        0 and 900, with the proviso that the sum m+n+q is other than 0.

Preferably, the sum m+n+q is between 1 and 100. Preferably, the summ+n+p+q is between 1 and 900 and better still between 1 and 800.Preferably, q is equal to 0.

-   -   the phenyl silicone oils corresponding to formula (VII) below,        and mixtures thereof:

in which:

-   -   R₁ to R₆, independently of each other, are saturated or        unsaturated, linear, cyclic or branched C₁-C₃₀ hydrocarbon-based        radicals,    -   m, n and p are, independently of each other, integers between 0        and 100, with the proviso that the sum n+m is between 1 and 100.

Preferably, R₁ to R₆, independently of each other, represent asaturated, linear or branched C₁-C₃₀ and especially C₁-C₁₂hydrocarbon-based radical and in particular a methyl, ethyl, propyl orbutyl radical.

R₁ to R₆ may especially be identical, and in addition may be a methylradical.

Preferably, m=1 or 2 or 3, and/or n=0 and/or p=0 or 1 may apply, informula (VII).

-   -   the phenyl silicone oils corresponding to formula (VIII) below,        and mixtures thereof:

in which:

-   -   R is a C₁-C₃₀ alkyl radical, an aryl radical or an aralkyl        radical,    -   n is an integer ranging from 0 to 100, and    -   m is an integer ranging from 0 to 100, with the proviso that the        sum n+m ranges from 1 to 100.

In particular, the radicals R of formula (VIII) and R₁ to R₁₀ definedpreviously may each represent a linear or branched, saturated orunsaturated alkyl radical, especially of C₂-C₂₀, in particular C₃-C₁₆and more particularly C₄-C₁₀, or a monocyclic or polycyclic C₆-C₁₄ andespecially C₁₀-C₁₃ aryl radical, or an aralkyl radical whose aryl andalkyl residues are as defined previously.

Preferably, R of formula (VIII) and R₁ to R₁₀ may each represent amethyl, ethyl, propyl, isopropyl, decyl, dodecyl or octadecyl radical,or alternatively a phenyl, tolyl, benzyl or phenethyl radical.

According to one embodiment, a phenyl silicone oil of formula (VIII)with a viscosity at 25° C. of between 5 and 1500 mm²/s (i.e. 5 to 1500cSt), and preferably with a viscosity of between 5 and 1000 mm²/s (i.e.5 to 1000 cSt) may be used.

As phenyl silicone oils of formula (VIII), it is especially possible touse phenyl trimethicones such as DC556 from Dow Corning (22.5 cSt), theoil Silbione 70663V30 from Rhône-Poulenc (28 cSt) or diphenyldimethicones such as Belsil oils, especially Belsil PDM1000 (1000 cSt),Belsil PDM 200 (200 cSt) and Belsil PDM 20 (20 cSt) from Wacker. Thevalues in parentheses represent the viscosities at 25° C.

-   -   the phenyl silicone oils corresponding to the following formula,        and mixtures thereof:

in which:

R₁, R₂, R₅ and R₆ are, together or separately, an alkyl radicalcontaining 1 to 6 carbon atoms,

R₃ and R₄ are, together or separately, an alkyl radical containing from1 to 6 carbon atoms or an aryl radical,

X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxylradical or a vinyl radical,

n and p being chosen so as to give the oil a weight-average molecularmass of less than 200 000 g/mol, preferably less than 150 000 g/mol andmore preferably less than 100 000 g/mol.

The phenyl silicones that are most particularly suitable for use in theinvention are those corresponding to formulae II, especially to formula(III), and V hereinabove.

More particularly, the phenyl silicones are chosen from phenyltrimethicones, phenyl dimethicones,phenyl-trimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyl trisiloxanes and 2-phenylethyl trimethylsiloxysilicates,and mixtures thereof.

Preferably, the weight-average molecular weight of the non-volatilephenyl silicone oil according to the invention ranges from 500 to 10 000g/mol.

Silicone Gum

According to another embodiment variant, a composition according to theinvention contains, as silicone compound, at least one silicone gum.

The silicone gum that may be used in the invention may be chosen fromsilicone gums with a viscosity at 25° C. of greater than or equal to 800000 centistokes (cSt) (8×10⁻⁶ m²/s), especially between 800 000 and 10000 000 cSt, preferably between 1 00 000 and 5 000 000 cSt andpreferably between 1 000 000 and 2 500 000 cSt. The viscosity of thissilicone gum may be measured according to standard ASTM D-445.

The molecular mass of the silicone gums is generally greater than 350000 g/mol, between 350 000 and 800 000 g/mol and preferably from 450 000to 700 000 g/mol.

The silicone gum may be chosen especially from the silicones of formula:

in which:

R₁, R₂, R₅ and R₆ are, together or separately, an alkyl radicalcontaining 1 to 6 carbon atoms,

R₃ and R₄ are, together or separately, an alkyl radical containing from1 to 6 carbon atoms, a vinyl radical, an amine radical or a hydroxylradical,

X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxylradical or an amine radical,

n and p being integers chosen such that the viscosity of the compound isgreater than 800 000 cSt.

As silicone gums that may be used according to the invention, mentionmay be made of those for which:

-   -   the substituents R₁ to R₆ represent a methyl group, the group X        represents a hydroxyl group, and n and p are such that the        molecular weight of the polymer is 600 000 g/mol, such as the        product sold under the name Mirasil C-DPDM by the company        Bluestar;    -   the substituents R₁ to R₆ represent a methyl group, the group X        represents a hydroxyl group, and n and p are such that the        molecular weight of the polymer is 600 000 g/mol, such as the        product sold under the name SGM 36 by the company Dow Corning;    -   dimethicones of the (polydimethylsiloxane) (methylvinylsiloxane)        type, such as SE63 sold by GE Bayer Silicones,        poly(dimethylsiloxane)(diphenyl)-(methylvinylsiloxane)        copolymers, and mixtures thereof.

A cosmetic makeup and/or care composition according to the inventionalso comprises the usual ingredients, as a function of the intended useof the composition.

Solid Fatty Substances

A composition according to the invention may also comprise at least onesolid fatty substance especially chosen from waxes and/or pasty fattysubstances.

Preferably, the amount of pasty substance in the makeup and/or carecomposition according to the invention is between 0.5% and 50% byweight, especially from 1% to 40% by weight or even 2% to 30% by weight,relative to the total weight of the composition.

Waxes

According to a first embodiment, the composition is free of wax.

According to a second embodiment, the composition comprises at least onewax.

The term “wax” means a lipophilic compound that is solid at roomtemperature (25° C.), with a reversible solid/liquid change of state,having a melting point of greater than or equal to 30° C., which may beup to 200° C. The waxes may be chosen from waxes of animal, plant,mineral or synthetic origin, and mixtures thereof. Mention may be madeespecially of hydrocarbon-based waxes, for instance beeswax, lanolin waxand Chinese insect waxes; rice bran wax, carnauba wax, candelilla wax,ouricury wax, alfalfa wax, berry wax, shellac wax, Japan wax and sumachwax; montan wax, orange wax, lemon wax, microcrystalline waxes,paraffins and ozokerite; polyethylene waxes, the waxes obtained byFisher-Tropsch synthesis and waxy copolymers, and also esters thereof.Mention may also be made of waxes obtained by catalytic hydrogenation ofanimal or plant oils containing linear or branched C₈-C₃₂ fatty chains.Among these, mention may be made especially of hydrogenated sunfloweroil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenatedlanolin oil and bis(1,1,1-trimethylolpropane) tetrastearate. Mention mayalso be made of silicone waxes and fluoro waxes. The waxes obtained byhydrogenation of castor oil esterified with cetyl alcohol may also beused.

Pasty Fatty Substances

According to a first embodiment, the composition is free of pasty fattysubstances.

According to a second embodiment, the composition comprises at least onepasty fatty substance.

The term “pasty fatty substance” refers to a lipophilic fatty compoundwith a reversible solid/liquid change of state and comprising, at atemperature of 23° C., a liquid fraction and a solid fraction. The pastycompound preferably has a hardness at 20° C. ranging from 0.001 to 0.5MPa and preferably from 0.002 to 0.4 MPa. The pasty compound ispreferably chosen from synthetic compounds and compounds of plantorigin. A pasty compound may be obtained by synthesis from startingmaterials of plant origin. Mention may be made especially, alone or as amixture, of:

-   -   lanolin and derivatives thereof, such as lanolin alcohol,        oxyethylenated lanolins, acetylated lanolin, lanolin esters such        as isopropyl lanolate, and oxypropylenated lanolins,    -   polymeric or non-polymeric silicone compounds, for instance        polydimethylsiloxanes of high molecular masses,        polydimethylsiloxanes containing side chains of the alkyl or        alkoxy type containing from 8 to 24 carbon atoms, especially        stearyl dimethicones,    -   polymeric or non-polymeric fluoro compounds,    -   vinyl polymers, especially olefin homopolymers; olefin        copolymers; hydrogenated diene homopolymers and copolymers;        linear or branched oligomers, homopolymers or copolymers of        alkyl (meth)acrylates preferably containing a C₈-C₃₀ alkyl        group; homopolymer and copolymer oligomers of vinyl esters        containing C8-C30 alkyl groups; homopolymer and copolymer        oligomers of vinyl ethers containing C8-C30 alkyl groups;    -   liposoluble polyethers resulting from polyetherification between        one or more C₂-C₁₀₀ and preferably C₂-C₅₀ diols; and especially        copolymers of ethylene oxide and/or of propylene oxide with        long-chain C₆-C₃₀ alkylene oxides, more preferably such that the        weight ratio of ethylene oxide and/or propylene oxide to the        alkylene oxides in the copolymer is 5/95 to 70/30;    -   polyol ethers chosen from polyalkylene glycol pentaerythrityl        ethers, fatty alcohol ethers of sugars, and mixtures thereof,        polyethylene glycol pentaerythrityl ether comprising five        oxyethylene (5 OE) units (CTFA name: PEG-5 pentaerythrityl        ether), polypropylene glycol pentaerythrityl ether comprising        five oxypropylene (5 OP) units (CTFA name: PPG-5 pentaerythrityl        ether), and mixtures thereof;    -   esters and polyesters; and especially (i) esters of a glycerol        oligomer, especially diglycerol esters, in particular        condensates of adipic acid and of glycerol, for which some of        the hydroxyl groups of the glycerols have reacted with a mixture        of fatty acids such as stearic acid, capric acid, stearic acid        and isostearic acid and 12-hydroxystearic acid; (ii) phytosterol        esters, (iii) pentaerythritol esters; (iv) esters formed from at        least one alcohol, at least one of the alcohols being a Guerbet        alcohol and from a diacid dimer formed from at least one        unsaturated fatty acid; (v) non-crosslinked polyesters resulting        from polycondensation between a linear or branched C₄-C₅₀        dicarboxylic acid or polycarboxylic acid and a C₂-C₅₀ diol or        polyol, (vi) polyesters resulting from the esterification, with        a polycarboxylic acid, of an aliphatic hydroxycarboxylic acid        ester; (vii) aliphatic esters of an ester resulting from the        esterification of an aliphatic hydroxycarboxylic acid ester with        an aliphatic carboxylic acid containing especially 4 to 30        carbon atoms. The aliphatic hydroxycarboxylic acid ester is        advantageously derived from a hydroxylated aliphatic carboxylic        acid containing 2 to 40 carbon atoms and 1 to 20 hydroxyl        groups; (viii) aliphatic esters of esters chosen from the ester        resulting from the esterification reaction of hydrogenated        castor oil with isostearic acid (hydrogenated castor oil mono-,        di- or triisostearate).

The pasty compound may also be of plant origin. Mention may be madeespecially of isomerized jojoba oil, such as trans-isomerized partiallyhydrogenated jojoba oil; orange wax, shea butter, partially hydrogenatedolive oil, cocoa butter and mango oil.

Aqueous Phase

A composition according to the invention may also comprise an aqueousphase, which may represent 0 to 80% by weight, especially 1% to 70% byweight or even 3% to 60% by weight relative to the total weight of thecomposition. This aqueous phase may be formed essentially from water, ormay comprise a mixture of water and of water-miscible solvent(miscibility in water of greater than 50% by weight at 25° C.) chosenespecially from monoalcohols containing 1 to 5 carbon atoms such asethanol, isopropanol, glycols containing 2 to 8 carbon atoms such aspropylene glycol, ethylene glycol, 1,3-butylene glycol, dipropyleneglycol, C3-C4 ketones and C2-C4 aldehydes, and mixtures thereof

However, as stated above, the compositions under consideration accordingto the invention are advantageously anhydrous or contain less than 3% byweight of water and preferably less than 1% by weight of water relativeto the total weight of the composition. The term “anhydrous” especiallymeans that water is preferably not deliberately added to thecomposition, but may be present in trace amount in the various compoundsused in the composition.

Surfactant(s)

A composition according to the invention may also comprise at least onesurfactant, which may be present in a proportion of from 0.1% to 10% byweight, especially 0.5% to 8% by weight, or even 1% to 6% by weightrelative to the total weight of the composition. The surfactant may bechosen from amphoteric, anionic, cationic and nonionic, preferablynonionic, surfactants. Mention may especially be made, alone or as amixture, of:

a) nonionic surfactants with an HLB of less than 8 at 25° C., optionallycombined with one or more nonionic surfactants with an HLB of greaterthan 8 at 25° C., as mentioned below, for instance:

-   -   saccharide esters and ethers such as sucrose stearates, sucrose        cocoate and sorbitan stearate, and mixtures thereof;    -   fatty acid esters, especially of C₈-C₂₄ and preferably of        C₁₆-C₂₂, and of polyol, especially of glycerol or sorbitol, such        as glyceryl stearate, glyceryl laurate, polyglyceryl-2 stearate,        sorbitan tristearate and glyceryl ricinoleate;    -   lecithins, such as soybean lecithins;    -   oxyethylenated and/or oxypropylenated ethers (which may comprise        1 to 150 oxyethylene and/or oxypropylene groups) of fatty        alcohols (especially of C₈-C₂₄ and preferably C₁₂-C₁₈ alcohols)        such as stearyl alcohol oxyethylene ether containing two        oxyethylene units (CTFA name: Steareth-2);    -   silicone surfactants, for instance dimethicone copolyols and        alkyldimethicone copolyols, for example the mixture of        cyclomethicone/dimethicone copolyol sold under the name        Q2-3225C® by the company Dow Corning;

b) nonionic surfactants with an HLB of greater than or equal to 8 at 25°C., for instance:

-   -   saccharide esters and ethers such as the mixture of cetylstearyl        glucoside and of cetyl and stearyl alcohols, for instance        Montanov 68 from SEPPIC;    -   oxyethylenated and/or oxypropylenated glycerol ethers, which may        comprise 1 to 150 oxyethylene and/or oxypropylene units;    -   oxyethylenated and/or oxypropylenated ethers (which may comprise        from 1 to 150 oxyethylene and/or oxypropylene units) of fatty        alcohols, especially of C₈-C₂₄ and preferably of C₁₂-C₁₅, such        as stearyl alcohol oxyethylene ether containing 20 oxyethylene        units (CTFA name: Steareth-20), cetearyl alcohol oxyethylene        ether containing 30 oxyethylene units (Ceteareth-30) and the        oxyethylene ether of the mixture of C₁₂-C₁₅ fatty alcohols        comprising seven oxyethylene units (C₁₂₋₁₅Pareth-7);    -   esters of a fatty acid, especially of C₈-C₂₄ and preferably of        C₁₆-C₂₂, and of polyethylene glycol (or PEG) (which may comprise        1 to 150 oxyethylene units), such as PEG-SO stearate and PEG-40        monostearate;    -   esters of a fatty acid, especially of C₈-C₂₄ and preferably of        C₁₆-C₂₂, and of oxyethylenated and/or oxypropylenated glycerol        ethers (which may comprise from 1 to 150 oxyethylene and/or        oxypropylene units), for instance glyceryl monostearate        polyoxyethylenated with 200 oxyethylene units; glyceryl stearate        polyoxyethylenated with 30 oxyethylene units, glyceryl oleate        polyoxyethylenated with 30 oxyethylene units, glyceryl cocoate        polyoxyethylenated with 30 oxyethylene units, glyceryl        isostearate polyoxyethylenated with 30 oxyethylene units and        glyceryl laurate polyoxyethylenated with 30 oxyethylene units;    -   esters of a fatty acid, especially of C₈-C₂₄ and preferably of        C₁₆-C₂₂, and of oxyethylenated and/or oxypropylenated sorbitol        ethers (which may comprise from 1 to 150 oxyethylene and/or        oxypropylene units), for instance polysorbate 20 and polysorbate        60;    -   dimethicone copolyol, especially the product sold under the name        Q2-5220® from Dow Corning;    -   dimethicone copolyol benzoate, such as the products sold under        the names Finsolv SLB 101® and 201® from Finetex;    -   copolymers of propylene oxide and of ethylene oxide, also known        as EO/PO polycondensates, which are copolymers formed from        polyethylene glycol and polypropylene glycol blocks, for        instance polyethylene glycol/polypropylene glycol/polyethylene        glycol triblock polycondensates.

c) anionic surfactants such as:

-   -   salts of C₁₆-C₃₀ fatty acids, especially amine salts, such as        triethanolamine stearate or 2-amino-2-methylpropane-1,3-diol        stearate;    -   polyoxyethylenated fatty acid salts, especially animated salts        or salts of alkali metals, and mixtures thereof;    -   phosphoric esters and salts thereof, such as DEA oleth-10        phosphate (Crodafos N 10N from the company Croda) or        monopotassium monocetyl phosphate; sulfosuccinates such as        disodium PEG-5 citrate lauryl sulfosuccinate and disodium        ricinoleamido MEA sulfosuccinate;    -   alkyl ether sulfates such as sodium lauryl ether sulfate;    -   isethionates;    -   acylglutamates such as disodium hydrogenated tallow glutamate        (Amisoft HS-21 R® from Ajinomoto) and sodium stearoyl glutamate        (Amisoft HS-11 PF® from Ajinomoto);    -   soybean derivatives, for instance potassium soyate;    -   citrates, for instance glyceryl stearate citrate;    -   proline derivatives, for instance sodium palmitoyl proline or        the mixture of sodium palmitoyl sarcosinate, magnesium palmitoyl        glutamate, palmitic acid and palmitoyl proline (Sepifeel One        from SEPPIC);    -   lactylates, for instance sodium stearoyl lactylate;    -   sarcosinates, for instance sodium palmitoyl sarcosinate or the        75/25 mixture of stearoyl sarcosine and myristoyl sarcosine;    -   sulfonates, for instance sodium C₁₄₋₁₇ alkyl-sec-sulfonate;    -   glycinates, for instance sodium cocoyl glycinate.

d) cationic surfactants such as:

-   -   alkylimidazolidiniums such as isostearylethylimidonium        ethosulfate,    -   ammonium salts such as (C₁₂₋₃₀ alkyl)tri(C₁₋₄ alkyl)ammonium        halides, for instance N,N,N-trimethyl-1-docosanaminium chloride        (or behentrimonium chloride);

e) amphoteric surfactants, for instance N-acylamino acids, such asN-alkylaminoacetates and disodium cocoamphodiacetate, and amine oxidessuch as stearamine oxide.

Additive(s)

A makeup and/or care composition according to the invention may alsocomprise at least one agent usually used in cosmetics, chosen, forexample, from reducing agents, thickeners, silicone elastomers,softeners, antifoams, moisturizers, UV-screening agents, ceramides;cosmetic active agents; peptizers, fragrances, proteins, vitamins,propellants, hydrophilic or lipophilic, film-forming or non-film-formingpolymers; lipophilic or hydrophilic gelling agents. The above additivesare generally present in an amount for each of them of between 0.01% and10% by weight relative to the total weight of the composition. Needlessto say, a person skilled in the art will take care to select theconstituents of the composition such that the advantageous propertiesassociated with the invention are not, or are not substantially,adversely affected.

Thickeners

Thus, a composition according to the invention may also comprise athickener. The thickener may be chosen from:

-   -   organomodified clays, which are clays treated with compounds        chosen especially from quaternary amines and tertiary amines.        Organomodified clays that may be mentioned include        organomodified bentonites, such as the product sold under the        name Bentone 34 by the company Rheox, and organomodified        hectorites such as the products sold under the names Bentone 27        and Bentone 38 by the company Rheox,    -   hydrophobic fumed silica. Such silicas are sold, for example,        under the references Aerosil R812® by the company Degussa and        Cab-O-Sil TS-530® by the company Cabot, and under the references        Aerosil R972® and Aerosil R974® by the company Degussa and        Cab-O-Sil TS-6100 and Cab-O-Sil TS-720® by the company Cabot.

The thickener may be present in a content ranging from 0.1% to 5% byweight and better still from 0.4% to 3% by weight relative to the totalweight of the composition.

Silicone Elastomers

According to another embodiment variant, a composition according to theinvention may also comprise at least one silicone elastomer, in otherwords an organopolysiloxane elastomer.

The term “organopolysiloxane elastomer” means a deformable, flexibleorganopolysiloxane with viscoelastic properties and especially theconsistency of a sponge or of a supple sphere. Its modulus of elasticityis such that this material withstands deformation and has limitedstretchability and contractability. This material is capable ofregaining its original shape after stretching.

It is more particularly a crosslinked organopolysiloxane elastomer.

Preferably, the organopolysiloxane elastomer is obtained by crosslinkingaddition reaction (A) of diorganopolysiloxane containing at least twohydrogens each bonded to a silicon, and (B) of diorganopolysiloxanecontaining at least two ethylenically unsaturated groups bonded tosilicon, especially in the presence (C) of a platinum catalyst, asdescribed, for instance, in patent application EP-A-295 886.

In particular, the organopolysiloxane elastomer may be obtained byreaction of a dimethylpolysiloxane with dimethylvinylsiloxy end groupsand of methylhydrogenopolysiloxane with trimethylsiloxy end groups, inthe presence of a platinum catalyst.

Compound (A) may especially be chosen from methylhydrogenopolysiloxanescontaining trimethylsiloxy end groups,dimethylsiloxane-methylhydrogenosiloxane copolymers containingtrimethylsiloxy end groups, dimethylsiloxane-methylhydrogenosiloxanecyclic copolymers.

The organopolysiloxanes (B) may be chosen in particular frommethylvinylpolysiloxanes, methylvinylsiloxane-dimethylsiloxanecopolymers, dimethylpolysiloxanes containing dimethylvinylsiloxy endgroups, dimethyl siloxane-methylphenylsiloxane copolymers containingdimethylvinylsiloxy end groups,dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymerscontaining dimethylvinylsiloxy end groups,dimethylsiloxane-methylvinylsiloxane copolymers containingtrimethylsiloxy end groups,dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymerscontaining trimethylsiloxy end groups,methyl(3,3,3-trifluoropropyl)polysiloxanes containingdimethylvinylsiloxy end groups, anddimethylsiloxane-methyl(3,3,3-trifluoropropyl)siloxane copolymerscontaining dimethylvinylsiloxy end groups.

It is advantageous for compound (A) to be added in an amount such thatthe molecular ratio between the total amount of hydrogen atoms bonded tosilicon atoms in compound (A) and the total amount of all theethylenically unsaturated groups in compound (B) is within the rangefrom 1.5/1 to 20/1.

Compound (C) is the catalyst for the crosslinking reaction, and isespecially chloroplatinic acid, chloroplatinic acid-olefin complexes,chloroplatinic acid-alkenylsiloxane complexes, chloroplatinicacid-diketone complexes, platinum black and platinum on a support.

The catalyst (C) is preferably added in an amount of from 0.1 to 1000parts by weight and better still from 1 to 100 parts by weight, as cleanplatinum metal, per 1000 parts by weight of the total amount ofcompounds (A) and (B).

The elastomer is advantageously a non-emulsifying elastomer.

The term “non-emulsifying” defines organopolysiloxane elastomers notcontaining a hydrophilic chain, and in particular not containing anypolyoxyalkylene units (especially polyoxyethylene or polyoxypropylene)or on any polyglyceryl units.

The organopolysiloxane elastomer particles are conveyed in the form of agel formed from an elastomeric organopolysiloxane included in at leastone hydrocarbon-based oil and/or one silicone oil. In these gels, theorganopolysiloxane particles are often non-spherical particles.

Non-emulsifying elastomers are especially described in patents EP 242219, EP 285 886 and EP 765 656 and in patent application JP-A-61-194009, the content of which is incorporated by way of reference.

Spherical non-emulsifying elastomers that may be used include those soldunder the names DC 9040, DC 9041, DC 9509, DC 9505 and DC 9506 by thecompany Dow Corning.

Organopolysiloxane elastomers with groups MQ, such as those sold by thecompany Wacker under the names Belsil RG100, Belsil RPG33 and,preferentially, RG80 may also be used in the compositions according tothe invention. The elastomer may also be an emulsifying elastomer.

The term “emulsifying organopolysiloxane elastomer” means anorganopolysiloxane elastomer comprising at least one hydrophilic chain,such as polyoxyalkylenated organopolysiloxane elastomers andpolyglycerolated silicone elastomers.

The emulsifying organopolysiloxane elastomer may be chosen frompolyoxyalkylenated organopolysiloxane elastomers.

The polyoxyalkylenated organopolysiloxane elastomer is a crosslinkedorganopolysiloxane elastomer that may be obtained by crosslinkingaddition reaction of diorganopolysiloxane containing at least onehydrogen bonded to silicon and of a polyoxyalkylene containing at leasttwo ethylenically unsaturated groups.

Advantageously, the polyoxyalkylenated organopolysiloxane elastomers maybe formed from divinyl compounds, in particular polyoxyalkylenescontaining at least two vinyl groups, which react with Si—H bonds of apolysiloxane.

Polyoxyalkylenated elastomers are especially described in patents U.S.Pat. No. 5,236,986, U.S. Pat. No. 5,412,004, U.S. Pat. No. 5,837,793 andU.S. Pat. No. 5,811,487, the content of which is incorporated byreference.

Polyoxyalkylenated organopolysiloxane elastomers that may be usedinclude those sold under the names KSG-21, KSG-20, KSG-30, KSG-31,KSG-32, KSG-33, KSG-210, KSG-310, KSG-320, KSG-330 and KSG-340 by thecompany Shin-Etsu, and DC9010 and DC9011 by the company Dow Corning.

The emulsifying organopolysiloxane elastomer may also be chosen frompolyglycerolated organopolysiloxane elastomers.

The polyglycerolated organopolysiloxane elastomer according to theinvention is an organopolysiloxane elastomer that may be obtained bycrosslinking addition reaction of diorganopolysiloxane containing atleast one hydrogen bonded to silicon and of polyglycerolated compoundscontaining ethylenically unsaturated groups, especially in the presenceof a platinum catalyst.

The polyglycerolated organopolysiloxane elastomer according to theinvention is conveyed in gel form in at least one hydrocarbon-based oiland/or one silicone oil. In these gels, the polyglycerolated elastomeris often in the form of non-spherical particles.

Polyglycerolated organopolysiloxane elastomers that may be used includethose sold under the names KSG-710, KSG-810, KSG-820, KSG-830 andKSG-840 by the company Shin-Etsu.

Non-emulsifying elastomers that may be used more particularly includethose sold under the names KSG-6, KSG-15, KSG-16, KSG-18, KSG-41,KSG-42, KSG-43 and KSG-44 by the company Shin-Etsu, DC9040 and DC9041 bythe company Dow Corning, and SFE 839 by the company General Electric.

Emulsifying elastomers that may be used more particularly include thosesold under the names KSG-31, KSG-32, KSG-33, KSG-210 and KSG-710 by thecompany Shin-Etsu.

Advantageously, the organopolysiloxane elastomer under considerationaccording to the invention is chosen from spherical non-emulsifyingorganopolysiloxane elastomers, polyglycerolated organopolysiloxaneelastomers and polyoxyalkylenated organopolysiloxane elastomers.

It is more particularly a polyoxyalkylenated organopolysiloxaneelastomer.

A makeup and/or care composition according to the invention mayespecially be in the form of a suspension, a dispersion, a solution, agel, an emulsion, especially an oil-in-water emulsion (O/W),water-in-oil emulsion (W/O) or multiple emulsion (W/O/W or polyol/O/W orO/W/O), or in the form of a cream, a mousse, a stick, a dispersion ofvesicles, especially of ionic or nonionic lipids, a two-phase ormulti-phase lotion, a spray, a powder or a paste.

Advantageously, as stated hereinabove, the compositions according to theinvention are anhydrous.

A person skilled in the art may select the appropriate galenical foiin,and also the method for preparing it, on the basis of his generalknowledge, taking into account firstly the nature of the constituentsused, especially their solubility in the support, and secondly theintended application of the composition.

In the description and in the examples that follow, unless otherwisementioned, the percentages are weight percentages and the ranges ofvalues given in the form “between . . . and . . . ” include the statedlower and upper limits.

The examples below are presented as non-limiting illustrations of thefield of the invention.

EXAMPLE 1 OF SYNTHESIS OF A SUPRAMOLECULAR POLYMER

100 g of dihydroxylated hydrogenated 1,2-polybutadiene polymer (GI3000from the company Nisso; Mn=4700 measured by GPC according to theprotocol described previously) are dried at 80° C., under reducedpressure, overnight. This polymer is dissolved in 400 ml of anhydroustoluene. 25 μl of catalyst (dibutyltin dilaurate) are added and themixture is heated at 80° C. with stirring, until a uniform solution isobtained. 15 g of isocyanate-functionalized molecule having thefollowing structure:

are added as a solution in 300 ml of anhydrous toluene, under acontrolled atmosphere at 40° C. The reaction mixture is heated to 100°C. and stirred at this temperature for 4 hours. The reaction ismonitored by infrared spectroscopy, with monitoring of the totaldisappearance of the characteristic peak for isocyanates at 2260 cm⁻¹.At the end of the reaction, 100 ml of ethanol are added to remove alltrace of residual isocyanate, and the mixture is then filtered, afterhaving added isododecane to make the solution less viscous. The polymersolution is then directly stripped with isododecane.

A solution of the final polymer in isododecane, with a solids content of21%, is obtained; the polymer is characterized by GPC (Mn=6400 andpolydispersity index=1.85) and 1H NMR (spectrum in accordance with whatis expected).

EXAMPLE 2 OF SYNTHESIS OF A SUPRAMOLECULAR POLYMER Synthesis of theUreidopyrimidone Difunctionalized Polymer G12000

106.1 g of dihydroxylated hydrogenated 1,2-polybutadiene polymer (GI2000from Nisso, Mn=3300 measured by GPC according to the protocol describedpreviously) are heated in the presence of 22 mg of catalyst (dibutyltindilaurate) at 80° C., under reduced pressure, for two hours. Thetemperature of the mixture is reduced to 20° C., under argon, followedby addition of 10 ml of isododecane and 19.3 g of isophoronediisocyanate (IPDI). The mixture is stirred for 16 hours at 20° C. undera controlled atmosphere, and is then heated to 120° C., followed byaddition of 25 ml of propylene carbonate. 12 g of 6-methylisocytosineare added, resulting in a uniform white suspension. This suspension isheated to 140° C. and stirred at this temperature for 6 hours. Thereaction is monitored by infrared spectroscopy, up to the totaldisappearance of the characteristic peak for isocyanates (2250 cm⁻¹).The mixture is then reduced to 30° C., and 400 ml of heptane, 200 ml ofTI-IF and 50 ml of ethanol are added, followed by filtration throughCelite. The mixture is then stripped with isododecane.

A solution of the polymer in isododecane, with a solids content of 25%,is finally obtained; the polymer is characterized by GPC (Mn=7000 andpolydispersity index=2.05).

EXAMPLE 3 OF SYNTHESIS OF A SUPRAMOLECULAR POLYMER

99 g of dihydroxylated hydrogenated 1,2-polybutadiene polymer (GI3000from Nisso, Mn=4700 measured by GPC according to the protocol describedpreviously) are heated in the presence of 22 mg of catalyst (dibutyltindilaurate) at 80° C., under reduced pressure, for two hours. Thetemperature of the mixture is reduced to 20° C., under argon, followedby addition of 30 ml of isododecane and 11 g of isophorone diisocyanate(IPDI). The mixture is stirred for 16 hours at 20° C. under a controlledatmosphere, and is then heated to 120° C., followed by addition of 25 mlof propylene carbonate. 8.1 g of 6-methylisocytosine are added,resulting in a homogeneous white suspension. This suspension is heatedto 140° C. and stirred at this temperature for 6 hours. The reaction ismonitored by infrared spectroscopy, up to the total disappearance of thecharacteristic peak for isocyanates (2250 cm⁻¹). The mixture is thenreduced to 30° C., and 1 liter of heptane is added, followed byfiltration through Celite. The mixture is then stripped withisododecane.

A solution of the polymer in isododecane, with a solids content of 20%,is finally obtained; the polymer is characterized by GPC (Mn=4200 andpolydispersity index=2.34).

EXAMPLE 4 OF SYNTHESIS OF A SUPRAMOLECULAR POLYMER

89 g of dihydroxylated hydrogenated 1,2-polybutadiene polymer (GI3000from Nisso, Mn=4700 measured by GPC according to the protocol describedpreviously) are heated in the presence of 22 mg of catalyst (dibutyltindilaurate) at 80° C., under reduced pressure, for two hours. Thetemperature of the mixture is reduced to 20° C., under argon, followedby addition of 60 ml of isododecane and 11.6 g of4,4′-dicyclohexylmethane diisocyanate. The mixture is stirred for 16hours at 20° C. under a controlled atmosphere, and is then heated to120° C., followed by addition of 40 ml of propylene carbonate. 6.64 g of6-methylisocytosine are added, resulting in a homogeneous whitesuspension. This suspension is heated to 140° C. and stirred at thistemperature for 8 hours. The reaction is monitored by infraredspectroscopy, up to the total disappearance of the characteristic peakfor isocyanates (2250 cm⁻¹). The mixture is then cooled to 30° C., and250 ml of isododecane and 500 ml of heptane are added, followed byfiltration through Celite. The mixture is then stripped withisododecane.

A solution of the polymer in isododecane, with a solids content of 22%,is finally obtained; the polymer is characterized by GPC (Mn=10 700 andpolydispersity index=2.26).

EXAMPLE 5 OF SYNTHESIS OF A SUPRAMOLECULAR POLYMER

143.1 g of dihydroxylated hydrogenated 1,2-polybutadiene polymer (GI2000from Nisso, Mn=3300 measured by GPC according to the protocol describedpreviously) are heated in the presence of 33 mg of catalyst (dibutyltindilaurate) at 80° C., under reduced pressure, for two hours. Thetemperature of the mixture is reduced to 20° C., under argon, followedby addition of 85 ml of isododecane and 30.8 g of4,4′-dicyclohexylmethane diisocyanate. The mixture is stirred for 16hours at 20° C. under a controlled atmosphere, and is then heated to120° C., followed by addition of 70 ml of propylene carbonate. 22.6 g of6-methylisocytosine are added, resulting in a homogeneous whitesuspension. This suspension is heated to 140° C. and stirred at thistemperature for 8 hours. The reaction is monitored by infraredspectroscopy, up to the total disappearance of the characteristic peakfor isocyanates (2250 cm⁻¹). The mixture is then cooled to 20° C., and700 ml of isododecane and 500 ml of heptane are added, followed byfiltration through Celite. The mixture is then stripped withisododecane.

A solution of the polymer in isododecane, with a solids content of 20%,is finally obtained; the polymer is characterized by GPC (Mn=8400 andpolydispersity index=2.00).

EXAMPLE 6 OF SYNTHESIS OF A POLY(ISOBORNYL ACRYLATE/ISOBORNYLMETHACRYLATE/ISOBUTYL ACRYLATE/ACRYLIC ACID) COPOLYMER

300 g of isododecane are placed in a 1 litre reactor, and thetemperature is then increased so as to go from room temperature (25° C.)to 90° C. in 1 hour.

105 g of isobornyl methacrylate, 105 g of isobornyl acrylate and 1.8 gof 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® 141 fromAkzo Nobel) are then added, at 90° C. and over 1 hour.

The mixture is maintained at 90° C. for 1 hour 30 minutes.

75 g of isobutyl acrylate, 15 g of acrylic acid and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are then added to thepreceding mixture, still at 90° C. and over 30 minutes.

The mixture is maintained at 90° C. for 3 hours and is then cooled.

A solution containing 50% of copolymer solids in isododecane isobtained.

A copolymer is obtained comprising a first poly(isobornylacrylate/isobornyl methacrylate) block with a Tg of 128° C., a secondpoly(isobutyl acrylate/acrylic acid) block with a Tg of −9° C. and anintermediate block, which is an isobornyl acrylate/isobornylmethacrylate/isobutyl acrylate/acrylic acid copolymer.

The Tg of the copolymer is 74° C.

These are theoretical Tg values calculated by Fox's law.

EXAMPLE 7 Effect of a Hydrophobic Film-Forming Polymer on the TransferResistance of Cosmetic Formulae of Foundation Type Applied to the Skin

Nine makeup formulae according to the invention having the followingcomposition were prepared (the percentages indicated are weightpercentages).

Table 1 below gives the formulation of these compositions.

TABLE 1 (formulae according to the invention) Formula 1 Formula 2Formula 3 Formula 4 Formula 5 Formula 6 In In In In In In accordanceaccordance accordance accordance accordance accordance with the with thewith the with the with the with the invention invention inventioninvention invention invention A1 Solution of ureidopyrimidone 48 (i.e.12% 48 (i.e. 12% 48 (i.e. 12% 48 (i.e. 12% 48 (i.e. 12% 48 (i.e. 12%difunctionalized polymer polymer polymer polymer polymer polymersupramolecular polymer solids)* solids)* solids)* solids)* solids)*solids)* GI2000 at 25% in isododecane, as prepared in Example 2Isododecane 32.5 12.5 29.2 25 27.5 17.5 A2 MQ resin (SR1000, 5Momentive) Nylon-611/Dimethicone 25 (i.e. 5% copolymer (DC 2-8179polymer Gellant, Dow Corning) solids)* prediluted to 20% in isododecaneAcrylates/Dimethicone 8.3 (i.e. 5 % ∘ copolymer diluted to 60% inpolymer isododecane (KP 550, solids)* Shin-Etsu) Butyl acrylatecopolymer ∘ 12.5 (i.e. 5 % containing dendritic silicone polymer sidechains diluted to 40% in solids)* isododecane (FA 4002 ID SiliconeAcrylate, Dow Corning) Acrylic acid/isobutyl 10 (i.e. 5%acrylate/isobornyl acrylate polymer copolymer diluted to 50% in solids)*isododecane (Mexomer PAS, Chimex) Acrylic copolymer as a 20 (i.e. 5 %dispersion in isododecane polymer with styrene/isoprene solids)*copolymer (Kraton G1701) diluted to 25% in isododecane (Mexomer PAP,Chimex) A3 Isododecane 2.5 2.5 2.5 2.5 2.5 2.5 Pigments 10 10 10 10 1010 B Amorphous silica 2 2 2 2 2 2 microspheres (particle size: 3microns) (Miyoshi Kasei, Sunsphere H-33, AGC Si-TECH) comparativeformulae Formula 7 Formula 8 Formula 9 Comparative supra polymerComparative of formula 2 Comparative of formula 6 (without film-formingpolymer) (without supra polymer) (without supra polymer) A1 Solution ofureidopyrimidone 68 (i.e. 17% polymer ∘ ∘ difunctionalizedsupramolecular solids)* polymer G12000 at 25% in isododecane, asprepared in Example 2 Isododecane 17.5 0.5 17.5 A2 MQ resin (SR1000,Momentive) Nylon-611/Dimethicone copolymer 85 (i.e. 17% solids) (DC2-8179 Gellant, Dow corning) prediluted to 20% in isododecaneAcrylates/Dimethicone copolymer diluted to 60% in isododecane (KP 550,Shin-Etsu) Butyl acrylate copolymer containing dendritic silicone sidechains diluted to 40% in isododecane (FA 4002 ID Silicone acrylate, DowCorning) Acrylic acid/isobutyl acrylate/ isobornyl acrylate copolymerdiluted to 50% in isododecane (Mexomer PAS, Chimex) Acrylic copolymer asa dispersion in 68 (i.e. 17% solids) isododecane with styrene/isoprenecopolymer (Kraton G1701) diluted to 25% in isododecane (Mexomer PAP,Chimex) A3 Isododecane 2.5 2.5 2.5 Pigments 10 10 10 B Amorphous silicamicrospheres 2 2 2 (particle size: 3 microns) (Miyoshi Kasei, SunsphereH-33, AGC Si-TECH)

Procedure:

The constituents of phase A3 are weighed out. The mixture is ground in athree-roll mill.

Next, the constituents of phase Al are weighed out in the main beakerand placed in a Rayneri blender. Phase A2 is then added, after whichphase A3 is added. After stirring for a few minutes, phase B isincorporated.

Each of the formulations thus obtained is then evaluated in terms oftransfer resistance according to the protocol described below.

Protocol for Evaluating the Transfer Resistance

The nine formulae are applied individually to the forearm according tothe following protocol.

The forearm is freed of makeup with a non-greasy makeup remover (such asEffacil from Lancôme) and then with cotton wool and water. After 5minutes, each foundation formula (formulae 1 to 9) is applied by fingerto the forearm. The amount applied is 0.05 g onto an area 5 cm by 5 cmin size.

10 minutes after the application, a paper tissue (handkerchief) is wipedfive times over the forearm in the following manner: the tissue isfolded into four, it is applied to the skin, with a suitable pressure,at one of the edges of the foundation and is then moved slowly towardsthe other edge. The amount of foundation deposit that has transferredonto the tissue is then evaluated.

For the measurements performed, it is considered that:

+ No colour on the handkerchief (i.e.: the composition shows very goodtransfer-resistance properties for the deposit)

++ The handkerchief is very slightly coloured (i.e.: the compositionshows good transfer-resistance properties for the deposit)

+++ The handkerchief is slightly coloured

++++ The handkerchief is coloured

+++++ The handkerchief is strongly coloured

The number of “+”s reflects the decreasing transfer-resistanceproperties (i.e. the more “+”s there are, the greater the makeup deposithas a tendency to transfer).

Table 2 below gives the results concerning the transfer evaluation.

TABLE 2 Formula Formula Formula Formula Formula Formula Formula FormulaFormula 1 2 3 4 5 6 7 8 9 (MQ resin) (Nylon- (Acrylates/ (Butyl (Acrylic(Acrylic Compara- Compara- Compara- 611/Dimeth Dimethi- acrylateacid/iso- copolymer tive supra tive of tive of icone cone copolymerbutyl as a polymer formula 2 formula 6 copolymer) copolymer containingacrylate/- dispersion (without (without (without diluted to dendriticisobornyl in isodo- film- supra supra 60% in silicone acrylate decaneforming polymer) polymer) isodo- side chains copolymer with polymer)decane) diluted to diluted to styrene/- 40% in 50% in isoprene isodo-isodo- copolymer decane) decane) (Kraton G1701) diluted to 25% in isodo-decane) ++ + ++ ++ ++ ++ ++++ ++++ ++++

It emerges from these results that the deposits of the compositions inaccordance with the invention show significantly less transfer tendencywhen compared with the comparative compositions (supramolecular polymeralone or film-forming polymer alone).

EXAMPLE 8 Cosmetic Lip Formulations

Four lip makeup formulae according to the invention having thecomposition below were prepared (the percentages indicated are weightpercentages).

Table 3 below gives the formulation of four compositions according tothe invention.

TABLE 3 Formula 13 Formula Formula Formula Comparative 10 11 12 supra InIn In polymer accordance accordance accordance (without with the withthe with the film-forming invention invention invention polymer)Solution of 41.6 41.6 41.6 71 ureidopyrimidone (i.e. 10.4% (i.e. 10.4%(i.e. 10.4% (i.e. 10.4% difunctionalized solids) solids) solids) solids)supramolecular polymer GI2000 at 25% in isododecane, as prepared inExample 2 Isododecane 50.05 50.05 50.05 28 Carmine 1 1 1 Acryliccopolymer as a 7.35 dispersion in isododecane with styrene/isoprenecopolymer (Kraton G1701) (Mexomer PAP from Chimex) (24.5% copolymersolids in isododecane) Trimethyl siloxysilicate 7.35 (MQ resin) (SR 1000from Momentive Performance Materials) Acrylate/Polytrimethyl 7.35siloxymethacrylate copolymer at 40% in isododecane (Dow Corning FA 4002ID Silicone Acrylate from Dow Corning)

Preparation Method:

A ground pigmentary material was prepared in some of the isododecane bygrinding the mixture three times in a three-roll mill

The ground material required for the composition was weighed out in abeaker.

The supramolecular polymer according to the invention was mixed with therest of the isododecane and the ground pigmentary material in a beakeror heating pan. Next, the mixture was stirred in a Rayneri blender untilhomogeneous.

Protocol for Evaluating the Resistance of the Deposit (FrictionResistance)

80-micron deposits were applied to an FP40 plate (butadiene nitrileelastomer support). The plates were then maintained at 37° C. for 24hours. After 24 hours, the deposits were wiped with makeup-removingwipes (L'Oréal Demaq'expert).

After wiping, the transfer on the wipe was significantly greater for thedeposit without combined hydrophobic film-forming compound, whereas inthe presence of hydrophobic film-forming compounds, the transfer wasvery light. This experiment confirmed that the combination of asupramolecular polymer with hydrophobic film-forming compounds makes itpossible to increase the resistance of the deposit to attack, especiallyto friction, and thus to reduce the transfer.

Protocol for Evaluating the Affinity of the Deposit with Sunflower Oil:(Fat Sensitivity)

80-micron deposits were applied to beige bioskin. The deposits were thenmaintained at 3TC for 24 hours.

After 24 hours, two drops of oil were then placed on the deposits andthe spreading of the drop of the deposit was observed. The more the dropspread, the greater was the contact angle and, consequently, the greaterwas the affinity of the oil for the deposit.

The spreading of the oil on the deposit was greater on the depositwithout hydrophobic film-forming compounds, which showed greateraffinity of the deposit for the oil. The addition of hydrophobicfilm-forming polymers made it possible to reduce the fat sensitivity. Itshould also be noted that the films with hydrophobic film-formingpolymers were significantly less tacky than the reference depositwithout hydrophobic film-forming polymers (before addition of oil andafter wiping with a paper handkerchief).

EXAMPLE 9 Cosmetic Formulation 14 of Liquid Lipstick Type

A lip makeup formula according to the invention having the followingcomposition was prepared (the percentages indicated are weightpercentages).

Preparation Method:

A ground pigmentary material was prepared in some of the isododecane bygrinding the mixture three times in a three-roll mill.

The ground material required for the composition was weighed out in abeaker.

The supramolecular polymer according to the invention was mixed with therest of the isododecane and the ground pigmentary material in a beakeror heating pan. Next, the mixture was stirred in a Rayneri blender untilhomogeneous.

TABLE 4 Formula 14 In accordance with the invention Solution ofureidopyrimidone difunctionalized 54 supramolecular polymer G12000 at25% in (i.e. 13.5% solids) isododecane, as prepared in Example 2Pigments 6.39 Phenyl trimethicone 22.61 (Dow Corning 556 Cosmetic GradeFluid from Dow Corning) Nacre 2 Acrylic copolymer as a dispersion in 15%isododecane with styrene/isoprene copolymer (i.e. 3.7% solids) (KratonG1701) (Mexomer PAP from Chimex) (24.5% copolymer solids in isododecane)

Protocol for Evaluating the Resistance of the Deposit to Attack(Friction Resistance)

80-micron deposits were applied to an FP40 plate (butadiene nitrileelastomer support). The plates were then maintained at 37° C. for 24hours. After 24 hours, the deposits were wiped with makeup-removingwipes (L'Oréal Demaq'expert).

After wiping, the transfer on the wipe was significantly greater for thefilm without hydrophobic film-forming compound, whereas in the presenceof hydrophobic film-forming compounds, the transfer was very light. Thisexperiment confirmed that the combination of a supramolecular polymerwith hydrophobic film-forming compounds makes it possible to increasethe resistance of the deposit to attack, especially to friction, andthus to reduce the transfer.

Protocol for Evaluating the Affinity of the Deposit for Sunflower Oil:(Fat Sensitivity)

80-micron deposits were applied to beige bioskin. The bioskins were thenmaintained at 37° C. for 24 hours.

After 24 hours, two drops of oil were then placed on the deposits andthe spreading of the drop of the deposit was observed. The more the dropspread, the greater was the contact angle and, consequently, the greaterwas the affinity of the oil for the deposit.

The spreading of the oil on the deposit was greater on the depositwithout hydrophobic film-forming compounds, which showed greateraffinity of the deposit for the oil. The addition of hydrophobicfilm-forming polymers made it possible to reduce the fat sensitivity. Itshould also be noted that the films with hydrophobic film-formingpolymers were significantly less tacky than the reference film withouthydrophobic film-forming polymers (before addition of oil and afterwiping with a paper handkerchief).

EXAMPLE 10 Cosmetic Formulations 15 and 16 of Liquid Lipstick Type

Two lip makeup formulae according to the invention having thecomposition below were prepared (the percentages indicated are weightpercentages).

TABLE 5 Formula Formula 15 16 In In accordance accordance with the withthe invention invention Solution of ureidopyrimidone 50 50difunctionalized supramolecular polymer (i.e. 12.5% (i.e. 12.5% G12000at 25% in isododecane, as solids) solids) prepared in Example 2 Pigment5 5 Phenyl trimethicone 30 15 (Dow Corning 556 Cosmetic Grade Fluid fromDow Corning) Block ethylenic copolymer at 50% in 15 (i.e. 7.5%isododecane as prepared in Synthetic solids) Example 6 (Mexomer PAS fromChimex) Acrylic copolymer as a dispersion in 30% (i.e. isododecane withstyrene/isoprene 7.35% copolymer (Kraton G1701) solids) (Mexomer PAPfrom Chimex) (24.5% copolymer solids in isododecane)

Preparation Protocol

A ground pigmentary material was prepared in some of the silicone oil bygrinding the mixture three times in a three-roll mill.

The ground material required for the composition was weighed out in abeaker.

The supramolecular polymer according to the invention was mixed with therest of the silicone oil, the film-forming compound and the groundpigmentary material in a beaker or heating pan. Next, the mixture wasstirred in a Rayneri blender until homogeneous.

Protocol for Evaluating the Resistance of the Deposit (FrictionResistance)

80-micron deposits were applied to an FP40 plate (butadiene nitrileelastomer support). The plates were then maintained at 37° C. for 24hours. After 24 hours, the deposits were wiped with makeup-removingwipes (L'Oréal Demaq'expert).

After wiping, the transfer on the wipe was significantly greater for thefilm without hydrophobic film-forming compound, whereas in the presenceof hydrophobic film-forming compounds, the transfer was very light. Thisexperiment confirmed that the combination of a supramolecular polymerwith hydrophobic film-forming compounds makes it possible to increasethe resistance of the deposit to attack, especially to friction, andthus to reduce the transfer.

Protocol for Evaluating the Affinity of the Deposit for Sunflower Oil:(Fat Sensitivity)

80-micron deposits were applied to beige bioskin. The bioskins were thenmaintained at 37° C. for 24 hours.

After 24 hours, two drops of oil were then placed on the deposits andthe spreading of the drop of the deposit was observed. The more the dropspread, the greater was the contact angle and, consequently, the greaterwas the affinity of the oil for the deposit.

The spreading of the oil on the deposit was greater on the depositwithout hydrophobic film-forming compounds, which showed greateraffinity of the deposit for the oil. The addition of hydrophobicfilm-forming polymers made it possible to reduce the fat sensitivity. Itshould also be noted that the films with hydrophobic film-formingpolymers were significantly less tacky than the reference film withouthydrophobic film-forming polymers (before addition of oil and afterwiping with a paper handkerchief).

1. A cosmetic process for making up and/or caring for skin and/or lips,comprising applying a cosmetic application to the skin and/or the lips,the cosmetic composition comprising, in a physiologically acceptablemedium: at least one supramolecular polymer based on functionalizedpolyalkene of formula HO—P—OH in which P represents a homopolymer or acopolymer that may be obtained by polymerization of one or more linear,cyclic and/or branched polyunsaturated C₂-C₁₀ alkenes, which may bederived from a reaction of the functionalized polyalkene polymer with atleast one junction group functionalized with at least one reactive groupcapable of reacting with reactive group(s) of the functionalizedpolyalkene polymer, the junction group being capable of forming at least3H(hydrogen) bonds; and at least one hydrophobic film-forming polymerchosen from polyamide silicone block polymers, block ethylenic polymers,vinyl polymers comprising at least one carbosiloxane dendrimerderivative, copolymers comprising carboxylate groups andpolydimethylsiloxane groups, silicone resins and lipodispersiblepolymers in the form of a non-aqueous dispersion of polymer particles,and mixtures thereof.
 2. The cosmetic process according to claim 1,wherein the functionalized polyalkene of formula HO—P—OH ishydrogenated.
 3. The cosmetic process according to claim 1, wherein Prepresents a homo- or copolymer that may be obtained by polymerizationof one or more linear and/or branched, C₂-C₄ diunsaturated alkenes. 4.The cosmetic process according to claim 1, wherein P represents apolybutylene, a polybutadiene, a polyisoprene, a poly(1,3-pentadiene) ora polyisobutylene, and copolymers thereof.
 5. The cosmetic processaccording to claim 1, wherein the functionalized junction group is offormula:

in which L represents a saturated or unsaturated C₁-C₂₀ divalentcarbon-based group.
 6. The cosmetic process according to claim 5,wherein L is chosen from a linear or branched C₁-C₂₀ alkylene; a C₅-C₂₀(alkyl)cycloalkylene, an alkylene-biscycloalkylene and a C₆-C₂₀(alkyl)arylene.
 7. The cosmetic process according to claim 1, whereinthe supramolecular polymer corresponds to the formula:

in which: L′ and L″ are, independently of each other, a saturated orunsaturated C₁-C₂₀ divalent carbon-based group; and —X, X′═O.
 8. Thecosmetic process according to claim 7, wherein: L′ and L″ are bothisophorone groups, P represents a polybutylene, a polybutadiene, apolyisoprene, a poly(1,3-pentadiene) or a polyisobutylene, andcopolymers thereof.
 9. The cosmetic process according to claim 1, thecomposition comprising from 0.1% to 60% by weight of supramolecularpolymer solids relative to the total weight of the composition.
 10. Thecosmetic process according to claim 1, wherein the hydrophobicfilm-forming polymer is at least one vinyl polymer bearing at least onecarbosiloxane dendrimer-based unit and is the product of polymerizationof: (A) 0 to 99.9 parts by weight of a vinyl monomer; and (B) 100 to 0.1part by weight of a carbosiloxane dendrimer containing aradical-polymerizable organic group, represented by the formula:

in which Y represents a radical-polymerizable organic group, R¹represents an aryl group or an alkyl group containing from 1 to 10carbon atoms, and X¹ represents a silylalkyl group which, when i=1, isrepresented by the formula:

in which R¹ is the same as defined above, R² represents an alkylenegroup containing from 2 to 10 carbon atoms, R³ represents an alkyl groupcontaining from 1 to 10 carbon atoms, X^(i+1) represents a hydrogenatom, an alkyl group containing from 1 to 10 carbon atoms, an arylgroup, or the silylalkyl group defined above with i=i+1; i is an integerfrom 1 to 10 that represents the generation of the said silylalkylgroup, and ai is an integer from 0 to 3; in which the saidradical-polymerizable organic group Y contained in components (B) ischosen from the group formed by an organic group that contains amethacrylic group or an acrylic group and that is represented by theformulae:

in which R⁴ represents a hydrogen atom or an alkyl group, R⁵ representsan alkylene group containing from 1 to 10 carbon atoms; and an organicgroups containing a styryl group and that is represented by the formula:

in which R⁶ represents a hydrogen atom or an alkyl group, R⁷ representsan alkyl group containing from 1 to 10 carbon atoms, R⁸ represents analkylene group containing from 1 to 10 carbon atoms, b is an integerfrom 0 to 4, and c is 0 or 1, such that if c is 0, —(R⁸)_(c)— representsa bond.
 11. The cosmetic process according to claim 10, wherein thevinyl polymer bearing at least one carbosiloxane dendrimer-based unit isan acrylate/polytrimethyl siloxymethacrylate copolymer.
 12. The cosmeticprocess according to claim 1, wherein the hydrophobic film-formingpolymer is at least one polyimide silicone block copolymer comprising atleast one unit of formula (III) or (IV):

in which: 1) R⁴, R⁵, R⁶ and R⁷, which may be identical or different,represent a group chosen from: linear, branched or cyclic, saturated orunsaturated, C₁ to C₄₀ hydrocarbon-based groups, possibly containing intheir chain one or more oxygen, sulfur and/or nitrogen atoms, andpossibly being partially or totally substituted with fluorine atoms,C₆-C₁₀ aryl groups, optionally substituted with one or more C₁-C₄ alkylgroups, polyorganosiloxane chains possibly containing one or moreoxygen, sulfur and/or nitrogen atoms; 2) the groups X, which may beidentical or different, represent a linear or branched C₁-C₃₀alkylenediyl group, possibly containing in its chain one or more oxygenand/or nitrogen atoms; 3) Y is a saturated or unsaturated C₁ to C₅₀linear or branched alkylene, arylene, cycloalkylene, alkylarylene orarylalkylene divalent group, which may comprise one or more oxygen,sulfur and/or nitrogen atoms, and/or may bear as substituent one of thefollowing atoms or groups of atoms: fluorine, hydroxyl, C₃ to C₈cycloalkyl, C_(i) to C₄₀ alkyl, C₅ to C₁₀ aryl, phenyl optionallysubstituted with 1 to 3 C₁ to C₃ alkyl, C₁ to C₃ hydroxyalkyl and C₁ toC₆ aminoalkyl groups, or 4) Y represents a group corresponding to theformula:

in which: T represents a linear or branched, saturated or unsaturated,C₃-C₂₄ trivalent or tetravalent hydrocarbon-based group optionallysubstituted with a polyorganosiloxane chain, and possibly containing oneor more atoms chosen from 0, N and S, or T represents a trivalent atomchosen from N, P and Al, and R⁸ represents a linear or branched C₁-C₅₀alkyl group or a polyorganosiloxane chain, possibly comprising one ormore ester, amide, urethane, thiocarbamate, urea, thiourea and/orsulfonamide groups, which may possibly be linked to another chain of thepolymer; and 5) n is an integer ranging from 2 to 500 and m is aninteger ranging from 50 to
 1000. 13. The cosmetic process according toclaim 1, wherein the hydrophobic film-forming polymer is at least onelipodispersible polymer in the form of a non-aqueous dispersion ofpolymer particles.
 14. The cosmetic process according to claim 1,wherein the hydrophobic film-forming polymer is at least one siliconeresin.
 15. The cosmetic process according to claim 1, wherein thehydrophobic film-forming polymer is at least one block ethyleniccopolymer containing at least a first block with a glass transitiontemperature (Tg) of greater than or equal to 40° C. and being totally orpartly derived from one or more first monomers, which are such that ahomopolymer prepared from the first monomers has a glass transitiontemperature of greater than or equal to 40° C., and at least a secondblock with a glass transition temperature of less than or equal to 20°C. and being derived totally or partly from one or more second monomers,which are such that a second homopolymer prepared from the secondmonomers has a glass transition temperature of less than or equal to 20°C., the first block and the second block being connected together via astatistical intermediate segment comprising at least one of the firstconstituent monomers of the first block and at least one of the secondconstituent monomers of the second block, and the block copolymer havinga polydispersity index I of greater than
 2. 16. The cosmetic process asclaimed in claim 15, wherein the block ethylenic copolymer is such thatthe first block is obtained from at least one acrylate monomer offormula CH₂═CH—COOR₂ in which R₂ represents a C₄ to C₁₂ cycloalkyl groupand from at least one methacrylate monomer of formula CH₂═C(CH₃)—COOR′₂in which R′₂ represents a C₄ to C₁₂ cycloalkyl group, and the secondblock being obtained from at least a second monomer with a glasstransition temperature of less than or equal to 20° C. and from anadditional monomer.
 17. The cosmetic process according to claim 1,wherein the hydrophobic film-forming polymer is a copolymer comprisingcarboxylate groups and polydimethylsiloxane groups.
 18. The cosmeticprocess according to claim 16, wherein the said hydrophobic film-formingpolymer is chosen from copolymers of acrylic acid and of stearylacrylate containing polydimethylsiloxane grafts, copolymers of stearylmethacrylate containing polydimethylsiloxane grafts, copolymers ofacrylic acid and of stearyl methacrylate containing polydimethylsiloxanegrafts, copolymers of methyl methacrylate, butyl methacrylate,2-ethylhexylacrylate and stearyl methacrylate containingpolydimethylsiloxane grafts.